CN111073347A - Preparation method of ultra-dispersed nano white carbon black for rubber filler - Google Patents

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

Info

Publication number
CN111073347A
CN111073347A CN201811217625.8A CN201811217625A CN111073347A CN 111073347 A CN111073347 A CN 111073347A CN 201811217625 A CN201811217625 A CN 201811217625A CN 111073347 A CN111073347 A CN 111073347A
Authority
CN
China
Prior art keywords
carbon black
white carbon
parts
nano white
butadiene rubber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201811217625.8A
Other languages
Chinese (zh)
Inventor
徐典宏
赵燕
牛承祥
王真琴
翟云芳
王在花
赵洪国
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Petrochina Co Ltd
Original Assignee
Petrochina Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Petrochina Co Ltd filed Critical Petrochina Co Ltd
Priority to CN201811217625.8A priority Critical patent/CN111073347A/en
Publication of CN111073347A publication Critical patent/CN111073347A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/32—Thermal properties
    • C01P2006/37—Stability against thermal decomposition
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a preparation method of ultra-dispersed nano white carbon black for rubber fillers. According to the method, firstly, alkylphenol polyoxyethylene ether and a silane coupling agent are subjected to copolymerization reaction, the product organosilicon/alkylphenol polyoxyethylene ether copolymer is generated to carry out multi-point anchoring modification on the surface of nano white carbon black particles, then solution polymerized styrene-butadiene rubber cement is subjected to acylation treatment, and finally the solution polymerized styrene-butadiene rubber cement is coated on the surface of the nano white carbon black particles to form a blocking layer with high connection strength so as to prepare the ultra-dispersed nano white carbon black. The method not only solves the problem that the nano white carbon black is agglomerated again under the conditions of long-term storage, high temperature and high shear, endows the nano white carbon black with super-dispersion property, but also improves the compatibility of the nano white carbon black and the solution polymerized styrene butadiene rubber, and ensures that the nano white carbon black particles can be uniformly dispersed into the solution polymerized styrene butadiene rubber system. The invention has low modification cost and little environmental pollution.

Description

Preparation method of ultra-dispersed nano white carbon black for rubber filler
Technical Field
The invention relates to a preparation method of ultra-dispersed nano white carbon black for rubber fillers.
Background
The nanometer white carbon black is porous substance, and the composition can be SiO2·nH2O represents, wherein nH2O exists in the form of surface hydroxyl, is white, non-toxic, amorphous and porous fine powder, has the characteristics of large inner surface volume, dispersibility, high temperature resistance, non-combustion, good electrical insulation property and the like, and has stable chemical property. The white carbon black is used as an environment-friendly auxiliary agent with excellent performance and is mainly used in the fields of rubber products and the like. The nano white carbon black has small particle size, large specific surface, high surface energy and a large amount of hydroxyl on the surface, so that the nano white carbon black is extremely easy to agglomerate and is difficult to disperse uniformly in the mixing process with the rubber material, thereby not only influencing the filling modification effect, but also damaging the performance of the rubber material.
At present, from the expected effect of the inorganic powder filling modified synthetic rubber, the smaller the particle size of the inorganic powder particles, the better the modification effect, but a technical problem inevitably occurs in the application process of the ultrafine inorganic powder, namely, the ultrafine powder is more difficult to be mixed, soaked and dispersed by rubber materials because the specific surface area is increased, the self-polymerization capacity is stronger and the particle size is reduced. Therefore, the problem of the dispersion of the ultrafine inorganic powder in the rubber has become a bottleneck in the preparation of high-performance rubber materials.
In the prior art, the nano white carbon black is modified by coupling agents or surfactants such as silane coupling agents, toluene isocyanate, inorganic minerals and oligomers, such as: CN101798473A discloses a preparation method of silane modified white carbon black, which comprises the steps of adding precipitated white carbon black and fumed white carbon black into a high-speed mixer according to the weight ratio of 3: 1-3: 2, slowly and uniformly adding polysulfide silane in a spraying manner, and gradually heating to 100-120 ℃ to promote surface modification reaction to obtain the silane modified white carbon black. CN101817529A discloses a preparation method of modified white carbon black, which comprises the steps of heating and activating white carbon black at 250-300 ℃ for 4-5 hours under the protection of nitrogen, mixing the activated white carbon black with toluene isocyanate, wherein the dosage of the toluene isocyanate is 10-20% of the dosage of the white carbon black, adding anhydrous xylene into the mixture, the mass ratio of the volume of the dosage of the anhydrous xylene to the dosage of the white carbon black is 5-8: 1, stirring and dispersing at room temperature under the protection of nitrogen, heating to 60-85 ℃, filtering, and drying to obtain the modified white carbon black. CN 1324885A discloses a halogen-free flame-retardant rubber material with excellent flame-retardant property prepared by modifying an inorganic flame-retardant filler with unsaturated carboxylic acid such as methacrylic acid (MAA) or Acrylic Acid (AA). CN101704967A discloses a preparation method of modified white carbon black, which comprises drying white carbon black at the temperature of 200-240 ℃ for 4-8 hours, plastifying the dried white carbon black with abietic acid type resin acid accounting for 4-7% of the weight of the white carbon black and chlorohydrin rubber accounting for 12-18% of the weight of the white carbon black at the temperature of 140-160 ℃ for 20-25 minutes, continuously extracting the white carbon black for 24 hours by tetrahydrofuran after discharging, and drying the white carbon black at the temperature of 120-150 ℃ after volatilizing the solvent to obtain the modified white carbon black. CN102558627A discloses a method for preparing white carbon black suspension, which comprises the steps of mixing white carbon black with water to obtain white carbon black-water suspension, wherein the mass ratio of the white carbon black to the water is 5% -20%, then carrying out surface treatment on the white carbon black in a water bath environment to enable the surface of the white carbon black to be organic, adjusting the pH value of the white carbon black-water suspension to 9-12, and finally uniformly mixing the white carbon black-water suspension with adjusted pH value with styrene butadiene latex to obtain styrene butadiene rubber liquid slurry added with the white carbon black. CN107189124A discloses a preparation method of modified white carbon black, which comprises the steps of drying white carbon black for 4-8 hours at the temperature of 200-240 ℃, plastifying the white carbon black with abietic acid type resin acid and chlorohydrin rubber for 20-25 minutes at the temperature of 140-160 ℃, continuously extracting for 24 hours by tetrahydrofuran after discharging, and drying to obtain the modified white carbon black. CN106589485A discloses a method for white carbon black suspension, which comprises the steps of mixing white carbon black with water to obtain white carbon black-water suspension, adjusting the temperature of the white carbon black suspension to 35-90 ℃ by a heating device, ensuring that the white carbon black suspension is in a flowing state in the period, adding a silane coupling agent into the white carbon black suspension, adding aliphatic polyoxyethylene ether (AEO) for modification, wherein the AEO accounts for 1-100% of the mass of the white carbon black, the silane coupling agent accounts for 1-100% of the mass of the white carbon black, and modifying the white carbon black for 0.5-10 hours by matching with high sound to form the white carbon black suspension with an O/W type emulsion structure. CN106832417A discloses a method for preparing organic white carbon black modified by aliphatic polyoxyethylene ether, which comprises the steps of mixing white carbon black with water to obtain white carbon black-water suspension, wherein the mass of the white carbon black accounts for 5% -20% of the total mass of the suspension, adjusting the temperature of the white carbon black suspension to be higher than the melting point of the aliphatic polyoxyethylene ether through heating equipment, ensuring that the white carbon black suspension is in a flowing state in the period, adding the aliphatic polyoxyethylene ether into the white carbon black suspension, fully modifying the white carbon black for 0.5-10 hours in a matching manner with high sound, ensuring that the white carbon black suspension is in a flowing state in the period, and finally dehydrating the modified white carbon black suspension to obtain dry modified white carbon black powder. CN1323687A discloses a preparation method of modified nano white carbon black, which comprises the steps of adding ethanol solution of silane coupling agent containing isocyanate group or amino group into gas phase nano white carbon black with average particle size of 1-40 nm, mixing uniformly, adding into oligomer polyol, heating to 220-240 ℃ under stirring, simultaneously vacuumizing to-0.095-0.098 Mpa, dehydrating and dealcoholizing for 2-3 hours; cooling to below 60 ℃, adding diisocyanate, and reacting for 1-2 hours at 70-80 ℃ and under the vacuum degree of-0.095-0.098 Mpa to obtain the nano white carbon black modified polyurethane prepolymer; then adding tetraethoxysilane and silane coupling agent containing isocyanate group or amino group as precursors into oligomer polyol, and taking hydrochloric acid as a catalyst to carry out hydrolysis and condensation, thereby generating the modified nano white carbon black in situ. CN106280491A discloses a preparation method of modified white carbon black, which is to add modified silicone oil into fumed silica and stir the mixture to obtain the modified fumed silica. CN201210347532.3 adopts siloxane coupling agent to process silicon dioxide through surface functionalization to prepare reactive nano silicon dioxide, and then uses in-situ emulsion polymerization to prepare nano silicon dioxide/poly conjugated diene composite emulsion with good stability.
In addition, graft polymer modification and inorganic material surface coating are adopted to modify nano white carbon black, and people of Stephania staciata and the like dissolve polyvinyl alcohol (PVA) with certain mass in water, heat and stir at 95 ℃ for 3 hours to prepare uniform solution, add White Carbon Black (WCB) water solution which is uniformly dispersed by high sound, stir uniformly, cool to room temperature, stand and defoam, pour the mixed solution into a mould, and carry out crosslinking by saturated boric acid solution to prepare WCB/PVA composite hydrogel (material guide 2016,30, 71-76). The polyacetal oligomer is prepared by condensation polymerization of paraformaldehyde and diethylene glycol by Pivotator et al, the surface of silica is activated by toluene-2, 4-diisocyanate, and then grafted with methylacryloyl (3-trimethoxy silane) propyl ester to modify the surface of the silica, and then a polystyrene layer is coated on the surface of the modified silica by soap-free polymerization (journal of macromolecules 2004,6, 835-. The Qiu Fang adopts gamma-methacryloxypropyltrimethoxysilane coupling agent (MPS) to modify nano-Silica (SiO)2) Then grafting polymethyl methacrylate (PMMA) through emulsion polymerization to obtain nano silicon dioxide particles (SiO) with a core-shell structure2MPS-PMMA) ("latex blending process" natural rubber/silica nanocomposite microstructure and performance control, 2010, master thesis at hainan university). Preparing polybutadiene/silicon dioxide nano composite material by using single osmunda japonica through an anion in-situ polymerization method, firstly treating the surface of nano white carbon black particles by adopting Y-methacryloxyphthalyloxy propyl trimethoxy silane (MPS)Then, the modified silica is dispersed in butadiene and cyclohexane solvent, n-butyllithium is added as an initiator after the high-sound dispersion, the polymerization reaction is carried out under the protection of nitrogen, and then the product is added into ethanol to obtain white precipitate, and the white precipitate is filtered and dried to obtain the modified silica nanocomposite (synthetic rubber industry, 2006, 29(6): 474).
Although the method improves the dispersibility of the nano white carbon black particles and enhances the compatibility with the rubber matrix, the methods still have certain limitations and have the defects of long reaction time, high energy consumption, complex operation and the like; when the nano white carbon black is modified by using the coupling agent or the surfactant, the defects of large using amount, high production cost, poor dispersion stability, easy re-agglomeration and the like exist.
Disclosure of Invention
The invention aims to provide a preparation method of ultra-dispersed nano white carbon black for rubber fillers. According to the method, firstly, alkylphenol polyoxyethylene ether and a silane coupling agent are subjected to copolymerization reaction, the product organosilicon/alkylphenol polyoxyethylene ether copolymer is generated to carry out multi-point anchoring modification on the surface of nano white carbon black particles, then solution polymerized styrene-butadiene rubber cement is subjected to acylation treatment, and finally the solution polymerized styrene-butadiene rubber cement is coated on the surface of the nano white carbon black particles to form a blocking layer with high connection strength so as to prepare the ultra-dispersed nano white carbon black. The method endows the nano white carbon black with super-dispersion property, not only solves the problem of easy agglomeration of the nano white carbon black, but also can prevent the problem of agglomeration again under the conditions of long-term storage, high temperature and high shear, simultaneously improves the compatibility of the nano white carbon black and the solution polymerized styrene butadiene rubber, and ensures that the nano white carbon black particles can be uniformly dispersed into the solution polymerized styrene butadiene rubber matrix.
The "parts" in the present invention mean parts by mass.
The invention relates to a preparation method of ultra-dispersed nano white carbon black for rubber filler, which comprises the following specific preparation steps:
(1) preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: taking the mass of the silane coupling agent as 100 parts, firstly adding 100 parts of the silane coupling agent and 100-200 parts of the solvent into a reactor, stirring for 1-2 hours, then adding 5-15 parts of alkylphenol polyoxyethylene ether, continuously stirring and heating until the temperature of the reactor reaches 50-70 ℃, rapidly adding 0.5-2.0 parts of initiator under the stirring condition, reacting for 5-10 hours, and then decompressing and distilling to obtain the organic silicon/alkylphenol polyoxyethylene ether.
(2) Preparing acylated solution polymerized styrene-butadiene rubber cement: taking the mass of the solution polymerized styrene-butadiene rubber cement as 100 parts, firstly adding 100 parts of solution polymerized styrene-butadiene rubber cement and 100-200 parts of solvent into a polymerization kettle, stirring and heating, when the temperature of the polymerization kettle reaches 40-50 ℃, rapidly adding 0.05-0.5 part of catalyst under the stirring condition, adding 5-15 parts of anhydride when the system becomes orange red, stirring and reacting for 2-4 h, adding 5-10 parts of terminator to terminate the reaction, filtering and washing to obtain the acylated solution polymerized styrene-butadiene rubber cement (the acetylation degree of the solution polymerized styrene-butadiene rubber cement is 0.5-5.0%).
(3) Preparing the ultra-dispersed nano white carbon black: taking 100 parts by mass of nano white carbon black, adding 100 parts by mass of nano white carbon black, 5-15 parts by mass of organic silicon/alkylphenol polyoxyethylene ether copolymer and 200-400 parts by mass of solvent into a polymerization kettle, heating to 40-60 ℃, and stirring for reaction for 1-3 hours; then adding 10-30 parts of acylation 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 ultra-dispersed nano white carbon black.
The white carbon black is nano-scale, and the particle size is as follows: 10 to 100 nm.
The alkylphenol ethoxylates disclosed by the invention are selected from at least one of Nonylphenol Polyoxyethylene Ether (NPEO), Octylphenol Polyoxyethylene Ether (OPEO), Dodecyl Polyoxyethylene Ether (DPEO) and dinonylphenol polyoxyethylene ether (DNPEO), and preferably NPEO.
The silane coupling agent of the present invention may be at least one selected from the group consisting of gamma-aminopropyltriethoxysilane (KH-550), 3-glycidoxypropyltrimethoxysilane (KH-560), vinyltriethoxysilane (A-151), N- β -aminoethyl-gamma-aminopropylmethyldimethoxysilane (KH-602), gamma-methacryloxypropyltrimethoxysilane (KH-570), N- β - (aminoethyl) -gamma-aminopropyltrimethoxysilane (KH-792), vinyltrimethoxysilane (A-171), and vinyltris (β -methoxyethoxy) silane (A-172), preferably KH-550.
The initiator is selected from at least one of sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium carbonate and sodium bicarbonate, and is preferably sodium hydroxide.
The solution polymerized styrene-butadiene rubber cement is prepared by the solution polymerization copolymerization of a conjugated diene compound and an aryl ethylene compound. Wherein the solid content of the solution polymerized styrene-butadiene rubber cement is 5-20 wt%.
The acid anhydride is a binary acid anhydride compound, is selected from at least one of Maleic Anhydride (MAH), succinic anhydride, maleic anhydride and phthalic anhydride, and is preferably MAH.
The catalyst is selected from anhydrous aluminum trichloride (AlCl)3) Boron trifluoride (BF)3) Tin tetrachloride (SnCl)4) Zinc dichloride (ZnCl)2) Preferably AlCl3The addition amount is 0.05-0.5 part, preferably 0.09-0.35 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 preferably cyclohexane.
The terminating agent of the present invention may be at least one selected from diethylhydroxylamine, hydroxylamine sulfate and sodium ferulate, and sodium ferulate is preferred.
The invention relates to a preparation method of super-dispersed nano white carbon black for rubber filler. The siloxane bond (-O-Si), ether bond (-R-O-R-) and hydroxyl (-OH) in the copolymer are used as anchoring groups, and are tightly connected with the hydroxyl on the surface of the white carbon black through the hydrogen bond effect, so that high-density polar anchoring points are formed on the surface of the white carbon black particles. And then, carrying out acylation reaction on the solution polymerized styrene-butadiene rubber cement by using binary anhydride so that the surface of the solution polymerized styrene-butadiene rubber cement is provided with a large number of polar group carboxyl groups. The polar anchoring point and the carboxyl on the surface of the acylated solution polymerized styrene-butadiene rubber cement generate strong 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.
Because the organic silicon/alkylphenol polyoxyethylene ether copolymer has a plurality of polar groups, the density of anchoring points is high, the connection strength is high, the solution polymerized styrene-butadiene rubber slurry coating layer is tightly connected with white carbon black particles, and the solution polymerized styrene-butadiene rubber slurry coating layer is difficult to separate even under the action of high temperature and high shear, and the solution polymerized styrene-butadiene rubber slurry chain structure of the coating layer has the non-polar characteristic, contains a benzene ring structure and has a large molecular steric hindrance effect, so that the nano white carbon black can stably exist in a single particle form under the mutual 'synergistic effect' (see attached figure 1). Meanwhile, the compatibility of the nano white carbon black and the solution polymerized styrene butadiene rubber is obviously improved, so that the nano white carbon black can be stably and uniformly dispersed in the solution polymerized styrene butadiene rubber matrix. 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). At a wave number of 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. In b, the wave number is 1200-1150 cm-1A sharp absorption peak of the ether group is generated, and the wave number is 1400-1390 cm-1A sharp absorption peak of carboxyl appears, and the wave number is 650-840 cm-1And a Si-O asymmetric secondary shrinkage vibration absorption peak appears, which indicates that the organic silicon/alkylphenol polyoxyethylene copolymer is deposited on the surface of the nano white carbon black particles.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The "parts" described in examples and comparative examples each refer to parts by mass.
⑴ sources of raw materials:
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
Nonylphenol Polyoxyethylene Ether (NPEO), Haian Yongsheng chemical Co., Ltd
Dodecyl Polyoxyethylene Ether (DPEO), Haian Yongsheng chemical Co., Ltd
Gamma-aminopropyltriethoxysilane (KH-550), Nanjing chemical Co., Ltd
Vinyltriethoxysilane (A-151), Nanjing chemical Co., Ltd
Anhydrous aluminum trichloride (AlCl)3) Ningboxin and chemical Co Ltd
Maleic Anhydride (MAH) with a purity of 99%, Tianjin City Fenghua factory
Other reagents are all commercial products
⑵ analytical test methods:
measurement of acetylation degree: the test was carried out using an infrared spectrometer of Shimadzu, Japan, model IR-460.
Infrared spectrum analysis of the sample: the functional group analysis is carried out on samples before and after the modification of the nano white carbon black by an infrared spectrometer of German Bruke spectral instrument company. Drying the sample in a vacuum oven at 100 ℃, tabletting by using potassium bromide, and collecting the sample with the wave number range of 400-4000cm-1。
Analyzing a sample by an electron microscope: and (3) carrying out dispersibility analysis on the sample before and after the modification of the nano white carbon black by adopting an XL-20 scanning electron microscope produced by Philips corporation in the Netherlands. And carrying out SEM analysis on the sample under the accelerating voltage of 20kV after the sample is subjected to gold spraying treatment by a surface treatment machine.
The method for measuring the sedimentation volume comprises the following steps: weighing 10g of modified nano white carbon black, placing the modified nano white carbon black into a graduated 100mL measuring cylinder, adding a certain amount of dispersant (liquid paraffin), adding the liquid paraffin to the 100mL scale after the modified nano white carbon black is completely soaked by the liquid paraffin, fully oscillating for 5min at the oscillation frequency of 30 times/1 min to ensure that the modified nano white carbon black is uniformly dispersed in the liquid paraffin, then standing, and reading the solid volume at different time. The sedimentation volume in the same time can reflect the compatibility between the particles and the organic solvent to a certain extent, and the sedimentation volume is large, so that the carbon black is well dispersed and is easy to be compatible.
Method for measuring oil absorption: referring to the determination method of oil absorption of aluminum hydroxide for YS/T618-2007 fillers, quantitative modified nano white carbon black is put into a watch glass, diisooctyl phthalate is dropwise added according to 0.2mL of the absolute value of each time, after each dropwise addition, the absolute value is fully ground by a knife until the powder can be bonded into large groups without cracking, and the oil absorption is V of the volume absorbed by each 100g of sample0(mL) as follows:
Figure BDA0001833952140000091
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 an organic silicon/alkylphenol polyoxyethylene ether copolymer: adding 100 parts of KH-550 and 100 parts of cyclohexane into a reactor, stirring for 1.0hr, then adding 5.0 parts of NPEO, continuously stirring and heating until the temperature of the reactor reaches 50 ℃, rapidly adding 0.5 part of sodium hydroxide under stirring, reacting for 5.0hr, and then decompressing and distilling to obtain the KH-550/NPEO copolymer a.
(2) Preparing acylated solution polymerized styrene-butadiene rubber cement: 100 portions of solution polymerized styrene-butadiene rubber cement SSBR2564s and 100 portions of CS are added into a polymerization kettle2Stirring and heating, and when the temperature of the polymerization kettle reaches 40 ℃, quickly adding 0.09 part of AlCl under the stirring condition3Adding 5 parts of MAH when the system becomes orange red, stirring and reacting for 2hr, adding 5 parts of sodium ferbamate to terminate the reaction, filtering, and washing to obtain the acylated solution polymerized styrene-butadiene rubber cement a (the acetylation degree is 1.2%).
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 5 parts of KH-550/NPEO copolymer a and 200 parts of cyclohexane into a polymerization kettle, heating to 40 ℃, and stirring for reacting for 1.0 hr; then 10 parts of acylation solution polymerized styrene-butadiene rubber cement a is added, after stirring reaction for 2.0 hours, the ultra-dispersed nano white carbon black is prepared by flash evaporation, drying and grinding. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 2
(1) Preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 1.
(2) Preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 1.
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 6 parts of KH-550/NPEO copolymer a and 230 parts of cyclohexane into a polymerization kettle, heating to 45 ℃, and stirring for reacting for 1.5 hours; then adding 14 parts of acylation 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 ultra-dispersed nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 3
(1) Preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 1.
(2) Preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 1.
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 8 parts of KH-550/NPEO copolymer a and 280 parts of cyclohexane into a polymerization kettle, heating to 45 ℃, and stirring for reacting for 1.9 hr; then 19 parts of acylation solution polymerized styrene-butadiene rubber cement a is added, after stirring reaction for 2.8 hours, the ultra-dispersed nano white carbon black is prepared by flash evaporation, drying and grinding. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 4
(1) Preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: adding 100 parts of KH-550 and 150 parts of cyclohexane into a reactor, stirring for 1.5 hours, then adding 10 parts of NPEO, continuously stirring and heating until the temperature of the reactor reaches 60 ℃, rapidly adding 1.5 parts of sodium hydroxide under the stirring condition, reacting for 8.0 hours, decompressing, distilling to obtain the KH-550/NPEO copolymer b.
(2) Preparing acylated solution polymerized styrene-butadiene rubber cement: 100 portions of solution polymerized styrene-butadiene rubber cement SSBR2564s and 150 portions of CS are added into a polymerization kettle2Stirring and heating, and when the temperature of the polymerization kettle reaches 45 ℃, quickly adding 0.3 part of AlCl under the stirring condition3Adding 11 parts of MAH until the system becomes orange red, stirring for reaction for 3 hours, adding 8 parts of sodium feramete to terminate the reaction, performing suction filtration, and washing to obtain the acylated solution polymerized styrene-butadiene rubber cement b (the acetylation degree is 2.9%).
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 10 parts of KH-550/NPEO copolymer b and 300 parts of cyclohexane into a polymerization kettle, heating to 50 ℃, and stirring for reacting for 2.0 hr; then 21 parts of acylation solution polymerized styrene-butadiene rubber cement b is added, after stirring reaction for 3.0 hours, the ultra-dispersed nano white carbon black is prepared by flash evaporation, drying and grinding. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 5
(1) Preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 4.
(2) Preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 4.
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 11 parts of KH-550/NPEO copolymer b and 320 parts of cyclohexane into a polymerization kettle, heating to 53 ℃, and stirring for reacting for 2.3 hours; then adding 23 parts of acylation solution polymerized styrene-butadiene rubber cement b, stirring and reacting for 3.2 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 6
(1) Preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 4.
(2) Preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 4.
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 12 parts of KH-550/NPEO copolymer b and 350 parts of cyclohexane into a polymerization kettle, heating to 55 ℃, and stirring for reacting for 2.5 hours; then adding 25 parts of acylation solution polymerized styrene-butadiene rubber cement b, stirring and reacting for 3.5 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 7
(1) Preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: adding 100 parts of A-151 and 200 parts of cyclohexane into a reactor, stirring for 2.0hr, then adding 15 parts of DPEO, continuously stirring and heating until the temperature of the reactor reaches 70 ℃, rapidly adding 2.0 parts of sodium hydroxide under stirring, reacting for 10hr, and then decompressing and distilling to obtain an A-151/DPEO copolymer c.
(2) Preparing acylated solution polymerized styrene-butadiene rubber cement: 100 portions of solution polymerized styrene-butadiene rubber cement SSBR2564s and 200 portions of CS are added into a polymerization kettle2Stirring and heating, and when the temperature of the polymerization kettle reaches 50 ℃, quickly adding 0.5 part of AlCl under the stirring condition3Adding 15 parts of MAH until the system becomes orange red, stirring for reacting for 4hr, adding 10 parts of sodium feramete to terminate the reaction, filtering, and washing to obtain the acylated solution polymerized styrene-butadiene rubber cement c (the acetylation degree is 4.1%).
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 13 parts of A-151/DPEO copolymer c and 370 parts of cyclohexane into a polymerization kettle, heating to 55 ℃, and stirring for reaction for 2.7 hours; then adding 27 parts of acylation solution polymerized styrene-butadiene rubber cement c, stirring and reacting for 3.7 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 8
(1) Preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 7.
(2) Preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 7.
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 14 parts of A-151/DPEO copolymer c and 390 parts of cyclohexane into a polymerization kettle, heating to 58 ℃, and stirring for reaction for 2.9 hours; then adding 29 parts of acylation solution polymerized styrene-butadiene rubber cement c, stirring and reacting for 3.8 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 9
(1) Preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 7.
(2) Preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 7.
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 15 parts of A-151/DPEO copolymer c and 400 parts of cyclohexane into a polymerization kettle, heating to 60 ℃, and stirring for reaction for 3.0 hours; then adding 30 parts of acylation 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 ultra-dispersed 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 an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 1.
(2) Preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 1.
(3) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 1 except that the amount of KH-550/NPEO copolymer a added during the preparation was 3.0 parts, namely: adding 100 parts of nano white carbon black (40nm), 3.0 parts of KH-550/NPEO copolymer a and 200 parts of cyclohexane into a polymerization kettle, heating to 40 ℃, and stirring for reacting for 1.0 hr; then 10 parts of acylation solution polymerized styrene-butadiene rubber cement a is added, after stirring reaction for 2.0 hours, the ultra-dispersed nano white carbon black is prepared by flash evaporation, drying and grinding. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 2
(1) Preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 2.
(2) Preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 2.
(3) Preparing the ultra-dispersed nano white carbon black: the other conditions are the same as example 2, except that the addition amount of the acylated solution polymerized styrene-butadiene rubber cement a in the preparation process is 7.0 parts, namely: adding 100 parts of nano white carbon black (40nm), 6 parts of KH-550/NPEO copolymer a and 230 parts of cyclohexane into a polymerization kettle, heating to 45 ℃, and stirring for reacting for 1.5 hours; then adding 7.0 parts of acylation 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 ultra-dispersed nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 3
(1) Preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 3.
(2) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 3, except that KH-550/NPEO copolymer a was not added during the preparation, but KH-550 was added directly, that is: adding 100 parts of nano white carbon black (40nm), 8 parts of KH-550 and 280 parts of cyclohexane into a polymerization kettle, heating to 45 ℃, and stirring for reacting for 1.9 hr; then 19 parts of acylation solution polymerized styrene-butadiene rubber cement a is added, after stirring reaction for 2.8 hours, the ultra-dispersed nano white carbon black is prepared by flash evaporation, drying and grinding. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 4
(1) Preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the other conditions were the same as in example 4 except that the amount of NPEO added during the preparation was 2.0 parts, that is: adding 100 parts of KH-550 and 150 parts of cyclohexane into a reactor, stirring for 1.5 hours, then adding 2.0 parts of NPEO, continuously stirring and heating until the temperature of the reactor reaches 60 ℃, rapidly adding 1.5 parts of sodium hydroxide under stirring, reacting for 8.0 hours, and then decompressing and distilling to obtain the KH-550/NPEO copolymer b-1.
(2) Preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 4.
(3) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 4, except that KH-550/NPEO copolymer b was not added during the preparation, but KH-550/NPEO copolymer b-1 was added, that is: adding 100 parts of nano white carbon black (40nm), 10 parts of KH-550/NPEO copolymer b-1 and 300 parts of cyclohexane into a polymerization kettle, heating to 50 ℃, and stirring for reaction for 2.0 hr; then 21 parts of acylation solution polymerized styrene-butadiene rubber cement b is added, after stirring reaction for 3.0 hours, the ultra-dispersed nano white carbon black is prepared by flash evaporation, drying and grinding. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 5
(1) Preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 5.
(2) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 5, except that the KH-550/NPEO copolymer b was not added during the preparation, but NPEO was added directly, i.e.: adding 100 parts of nano white carbon black (40nm), 11 parts of NPEO and 320 parts of cyclohexane into a polymerization kettle, heating to 53 ℃, and stirring for reaction for 2.3 hours; then adding 23 parts of acylation solution polymerized styrene-butadiene rubber cement b, stirring and reacting for 3.2 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 6
(1) Preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 6.
(2) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 6, except that no KH-550/NPEO copolymer b was added during the preparation, i.e.: adding 100 parts of nano white carbon black (40nm) and 350 parts of cyclohexane into a polymerization kettle, heating to 55 ℃, and stirring for reacting for 2.5 hours; then adding 25 parts of acylation solution polymerized styrene-butadiene rubber cement b, stirring and reacting for 3.5 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 7
(1) Preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 7.
(2) Preparing acylated solution polymerized styrene-butadiene rubber cement: the other conditions were the same as in example 7 except that the amount of MAH added during the preparation was 4.0 parts, that is: 100 portions of solution polymerized styrene-butadiene rubber cement SSBR2564s and 200 portions of CS are added into a polymerization kettle2Stirring and heating, and when the temperature of the polymerization kettle reaches 50 ℃, quickly adding 0.5 part of AlCl under the stirring condition3Adding 4.0 parts of MAH until the system becomes orange red, stirring for reaction for 4hr, adding 10 parts of sodium feramete to terminate the reaction, filtering, and washing to obtain the acylated solution polymerized styrene-butadiene rubber cement c-1 (acetylation degree of 0.3%).
(3) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 7, except that the preparation process was carried out without adding the acylated solution-polymerized styrene-butadiene rubber cement c, but with adding the acylated solution-polymerized styrene-butadiene rubber cement c-1, namely: adding 100 parts of nano white carbon black (40nm), 13 parts of A-151/DPEO copolymer c and 370 parts of cyclohexane into a polymerization kettle, heating to 55 ℃, and stirring for reaction for 2.7 hours; then adding 27 parts of acylation solution polymerized styrene-butadiene rubber cement c-1, stirring and reacting for 3.7 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 8
(1) Preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 8.
(2) Preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 8.
(3) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 8, except that the solution-polymerized styrene-butadiene rubber cement SSBR2564s was directly added without adding the acylated solution-polymerized styrene-butadiene rubber cement c in the preparation process, namely: adding 100 parts of nano white carbon black (40nm), 14 parts of A-151/DPEO copolymer c and 390 parts of cyclohexane into a polymerization kettle, heating to 58 ℃, and stirring for reaction for 2.9 hours; then adding 29 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s, stirring and reacting for 3.8 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 9
(1) Preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the other conditions were the same as in example 9 except that the amount of DPEO added during the preparation was 4.0 parts, that is: adding 100 parts of A-151 and 200 parts of cyclohexane into a reactor, stirring for 2.0hr, then adding 4.0 parts of DPEO, continuously stirring and heating until the temperature of the reactor reaches 70 ℃, rapidly adding 2.0 parts of sodium hydroxide under stirring, reacting for 10hr, and then decompressing and distilling to obtain the A-151/DPEO copolymer c-1.
(2) Preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 9.
(3) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 9, except that the A-151/DPEO copolymer c was not added during the preparation, but the A-151/DPEO copolymer c-1 was added, namely: adding 100 parts of nano white carbon black (40nm), 15 parts of A-151/DPEO copolymer c-1 and 400 parts of cyclohexane into a polymerization kettle, heating to 60 ℃, and stirring for reaction for 3.0 hr; then adding 30 parts of acylation 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 ultra-dispersed 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 rate of ultra-dispersed nano white carbon black
Figure BDA0001833952140000171
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 ultra-dispersed nano white carbon black for rubber filler is characterized by comprising the following modification steps:
(1) preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: adding 100 parts by mass of silane coupling agent and 100-200 parts by mass of solvent into a reactor, stirring for 1-2 hours, then adding 5-15 parts by mass of alkylphenol polyoxyethylene ether, continuously stirring and heating until the temperature of the reactor reaches 50-70 ℃, rapidly adding 0.5-2.0 parts by mass of initiator under the stirring condition, reacting for 5-10 hours, and then decompressing and distilling to obtain organic silicon/alkylphenol polyoxyethylene ether;
(2) preparing acylated solution polymerized styrene-butadiene rubber cement: adding 100 parts by mass of solution polymerized styrene-butadiene rubber cement and 100-200 parts by mass of solvent into a polymerization kettle, stirring and heating, when the temperature of the polymerization kettle reaches 40-50 ℃, rapidly adding 0.05-0.5 part by mass of catalyst under the stirring condition, adding 5-15 parts by mass of anhydride until the system becomes orange red, stirring and reacting for 2-4 hours, adding 5-10 parts by mass of terminator to terminate the reaction, and performing suction filtration and washing to obtain acylated solution polymerized styrene-butadiene rubber cement;
(3) preparing the ultra-dispersed nano white carbon black: adding 100 parts by mass of nano white carbon black, 5-15 parts by mass of organic silicon/alkylphenol polyoxyethylene ether copolymer and 200-400 parts by mass of solvent into a polymerization kettle, heating to 40-60 ℃, and stirring for reaction for 1-3 hours; then adding 10-30 parts by mass of acylated solution polymerized styrene-butadiene rubber cement, stirring and reacting for 2-4 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black.
2. The method according to claim 1, wherein the nano white carbon black has a particle size of 10 to 100 nm.
3. The method of claim 1, wherein the alkylphenol ethoxylate is at least one member selected from the group consisting of nonylphenol ethoxylate, octylphenol ethoxylate, dodecylphenol ethoxylate, and dinonylphenol ethoxylate.
4. The method of claim 3, wherein said alkylphenol ethoxylate is dinonylphenol ethoxylate.
5. The method according to claim 1, wherein the silane coupling agent is at least one member selected from the group consisting of gamma-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltriethoxysilane, N- β -aminoethyl-gamma-aminopropylmethyldimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, N- β - (aminoethyl) -gamma-aminopropyltrimethoxysilane, vinyltrimethoxysilane, and vinyltris (β -methoxyethoxy) silane.
6. The method of claim 5, wherein the silane coupling agent is gamma-aminopropyltriethoxysilane.
7. The method of claim 1, wherein the initiator is selected from at least one of sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium carbonate, and sodium bicarbonate.
8. The method of claim 7, wherein said initiator is sodium hydroxide.
9. The method according to claim 1, wherein the solution-polymerized styrene-butadiene rubber cement has a solid content of 5 to 20 wt%.
10. The method of claim 1, wherein the acid anhydride is a dibasic acid anhydride compound selected from at least one of maleic anhydride, succinic anhydride, maleic anhydride, and phthalic anhydride.
11. The method of claim 10, wherein the anhydride is maleic anhydride.
12. The method of claim 1, wherein the catalyst is selected from at least one of the group consisting of anhydrous aluminum trichloride, boron trifluoride, tin tetrachloride, and zinc dichloride.
13. The process of claim 1 wherein the catalyst is anhydrous aluminum trichloride.
14. The method according to claim 12 or 13, wherein the catalyst is added in an amount of 0.09 to 0.35 parts by mass.
CN201811217625.8A 2018-10-18 2018-10-18 Preparation method of ultra-dispersed nano white carbon black for rubber filler Pending CN111073347A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811217625.8A CN111073347A (en) 2018-10-18 2018-10-18 Preparation method of ultra-dispersed nano white carbon black for rubber filler

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811217625.8A CN111073347A (en) 2018-10-18 2018-10-18 Preparation method of ultra-dispersed nano white carbon black for rubber filler

Publications (1)

Publication Number Publication Date
CN111073347A true CN111073347A (en) 2020-04-28

Family

ID=70308918

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811217625.8A Pending CN111073347A (en) 2018-10-18 2018-10-18 Preparation method of ultra-dispersed nano white carbon black for rubber filler

Country Status (1)

Country Link
CN (1) CN111073347A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115466433A (en) * 2021-06-11 2022-12-13 中国石油天然气股份有限公司 Rare earth element separant modified nano white carbon black and preparation method thereof
CN116804129A (en) * 2023-08-01 2023-09-26 广州翔铭环保新材料有限公司 Water-based 2K piano black finish paint and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988000608A1 (en) * 1986-07-22 1988-01-28 E.C.C. America Inc. Process for surface treating layered lattice silicates and resultant products
CN101220177A (en) * 2008-01-25 2008-07-16 北京化工大学 Process for producing white carbon black/solution polymerized butadiene styrene rubber nano-composite material
CN107074014A (en) * 2014-08-11 2017-08-18 固铂轮胎与橡胶公司 The functionalized SiO 2 of flexible body adhesive

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988000608A1 (en) * 1986-07-22 1988-01-28 E.C.C. America Inc. Process for surface treating layered lattice silicates and resultant products
CN101220177A (en) * 2008-01-25 2008-07-16 北京化工大学 Process for producing white carbon black/solution polymerized butadiene styrene rubber nano-composite material
CN107074014A (en) * 2014-08-11 2017-08-18 固铂轮胎与橡胶公司 The functionalized SiO 2 of flexible body adhesive

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115466433A (en) * 2021-06-11 2022-12-13 中国石油天然气股份有限公司 Rare earth element separant modified nano white carbon black and preparation method thereof
CN116804129A (en) * 2023-08-01 2023-09-26 广州翔铭环保新材料有限公司 Water-based 2K piano black finish paint and preparation method thereof
CN116804129B (en) * 2023-08-01 2024-03-26 广州翔铭环保新材料有限公司 Water-based 2K piano black finish paint and preparation method thereof

Similar Documents

Publication Publication Date Title
CN108192138B (en) Modification method of carbon nano tube used as rubber filler
CN108192141B (en) Modification method of rubber filler carbon nano tube
CN111073347A (en) Preparation method of ultra-dispersed nano white carbon black for rubber filler
Wang et al. Synthesis and characterization of nanosilica/polyacrylate composite latex
CN115124838B (en) Polysulfone/modified filler composite dielectric film material and preparation method thereof
CN111073354A (en) Method for modifying ultra-dispersion of rubber filler nano white carbon black
Yuvaraj et al. Organic–inorganic polypyrrole‐surface modified SiO2 hybrid nanocomposites: a facile and green synthetic approach
CN111073353A (en) Preparation method of ultra-dispersed nano white carbon black used as rubber filler
CN111073049A (en) Modification method of nano white carbon black used as rubber filler
CN111073045A (en) Modification method of high-dispersion rubber filler nano white carbon black
CN108192143B (en) Method for modifying carbon nano tube used as rubber filler
CN108299579B (en) Graphene/nano silicon dioxide/polystyrene hybrid material and preparation method and application thereof
CN108192140B (en) Modification method for high-dispersion carbon nano tube of rubber filler
CN111073048A (en) Preparation method of high-dispersion rubber filler nano white carbon black
CN111073050A (en) Preparation method of nano white carbon black for high-dispersion rubber filler
CN111073046A (en) Modification method for high dispersion of rubber filler nano white carbon black
CN111073349A (en) Preparation method of high-dispersion nano white carbon black for rubber filler
CN111073043A (en) Preparation method of high-dispersion nano white carbon black for filling rubber
CN111073052A (en) Preparation method of ultra-dispersed nano white carbon black
CN111073197A (en) Preparation method of high-dispersion nano white carbon black used as rubber filler
Zhai et al. Deformation of raspberry-like polymer composite particles by colloidal fusion
CN108192142B (en) Modification method of high-dispersion carbon nano tube used as rubber filler
CN111073042A (en) Preparation method of ultra-dispersed nano white carbon black for rubber filler
CN111073051A (en) Preparation method of nano white carbon black used as rubber filler
CN111073047A (en) Modification method of nano white carbon black used as rubber filler

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200428