CN111073042A - 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 PDFInfo
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Abstract
The invention provides a preparation method of ultra-dispersed nano white carbon black for rubber fillers. Firstly, carrying out copolymerization reaction on alkylphenol polyoxyethylene ether and a silane coupling agent to generate a product, namely organic silicon/alkylphenol polyoxyethylene ether copolymer, carrying out multi-point anchoring modification on the surface of nano white carbon black particles, then carrying out polarity pre-emulsification treatment on an unsaturated acrylate polar monomer and an aryl ethylene monomer, and preparing the ultra-dispersed nano white carbon black by utilizing in-situ polymerization. The method endows the nano white carbon black with super-dispersibility, not only solves the problem that the nano white carbon black is easy to agglomerate again due to long-term storage, high temperature and high shear conditions, 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 matrix. The invention has low modification cost and little environmental pollution.
Description
Technical Field
The invention relates to a preparation method of ultra-dispersible rubber filler nano white carbon black.
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 the nano white carbon black, such as: the polyacetal oligomers were prepared by condensation polymerization of paraformaldehyde with diethylene glycol, and grafted with toluene-2, 4-diisocyanate after surface activation of silica (proceedings of university of south China university of science 2005,29, 33-333). The surface of silicon dioxide is modified by methacryloyl (3-trimethoxy silane) propyl ester by Huangfain et al, and then a polystyrene layer is coated on the surface of the modified silicon dioxide by soap-free polymerization (polymer academic newspaper 2004,6, 835-835). 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. Firstly, carrying out copolymerization reaction on alkylphenol polyoxyethylene ether and a silane coupling agent to generate a product, namely organic silicon/alkylphenol polyoxyethylene ether copolymer, carrying out multi-point anchoring modification on the surface of nano white carbon black particles, then carrying out polarity pre-emulsification treatment on an unsaturated acrylate polar monomer and an aryl ethylene monomer, and preparing the ultra-dispersed nano white carbon black by utilizing in-situ polymerization. The method endows the nano white carbon black with super-dispersibility, not only solves the problem that the nano white carbon black is easy to agglomerate again due to long-term storage, high temperature and high shear conditions, 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 matrix.
The "parts" in the present invention mean parts by mass.
The invention relates to a method for modifying the ultra-dispersion of rubber filler nano white carbon black, 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 4-13 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 catalyst under the stirring condition, reacting for 5-10 hours, and then decompressing and distilling to obtain the organic silicon/alkylphenol polyoxyethylene ether.
(2) Preparing a polar monomer pre-emulsion: according to the mass percentage of the aryl ethylene monomer, 100 parts of the aryl ethylene monomer, 5-10 parts of unsaturated acrylate polar monomer, 1-5 parts of emulsifier and 100-200 parts of deionized water are put into a reaction kettle and stirred and mixed for 10-30 min; then adding 1.0-2.0 parts of buffering agent and 0.05-0.2 part of initiator, heating to 40-60 ℃, stirring and reacting for 1-3 hr to prepare the polar monomer pre-emulsion.
(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 4-12 parts of polar monomer pre-emulsion, 200-300 parts of deionized water, 2-6 parts of emulsifier and 1-3 parts of buffering agent, stirring and heating to 70-80 ℃, mixing for 30-50 min to generate a polymer which takes nano white carbon black powder as the center and is coated by organic silicon/alkylphenol polyoxyethylene ether copolymer and polar monomer pre-emulsion, and taking the polymer as a seed; and finally, adding 20-40 parts of aryl ethylene monomer and 0.1-0.5 part of initiator, reacting for 5.0-10 hr, adding 0.1-0.5 part of terminator, washing, dehydrating, 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 ethoxylate provided by the invention is selected from one of nonylphenol ethoxylate (NPEO), octylphenol ethoxylate (OPEO), dodecylphenol ethoxylate (DPEO) and dinonylphenol ethoxylate (DNPEO), and preferably DNPEO.
The silane coupling agent of the present invention may be 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 A-171.
The catalyst is selected from one of sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium carbonate and sodium bicarbonate, and is preferably sodium hydroxide.
The aryl ethylene compound can be one or a mixture of more of styrene, α -methyl styrene, 2-phenylpropylene, ethyl styrene and derivatives thereof, and styrene is preferred.
The unsaturated carboxylic acid polar monomer is selected from one or a mixture of Methyl Methacrylate (MMA), ethyl methacrylate, butyl methacrylate or tert-butyl methacrylate, and preferably MMA.
The initiator is a water-soluble thermal initiator and is selected from one of ammonium persulfate, potassium persulfate and sodium persulfate, and potassium persulfate is preferred.
The emulsifier, the buffer, the terminating agent and the like used in the present invention can all adopt conventional auxiliary agents commonly used in the field, and the addition amount thereof is also a conventional amount which can be calculated by a person skilled in the art according to the amount of the latex, and the present invention is not particularly limited. The emulsifier according to the present invention is well known to those skilled in the art, and may be one or more of an anionic emulsifier and a nonionic emulsifier. Such as: can be selected from one or more of fatty acid soap, abietic acid soap, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, and polyoxyethylene sorbitan monooleate, and is preferably sodium dodecyl benzene sulfonate.
The buffer of the present invention may be one selected from sodium carbonate, sodium bicarbonate, sodium hydroxide, ammonia water and ammonium bicarbonate, and sodium hydroxide is preferred.
The terminating agent of the invention can be selected from one or more of diethylhydroxylamine, hydroxylamine sulfate and sodium fermet.
The solvent according to the invention may be selected from cyclohexane, carbon disulphide (CS)2) Nitrobenzene, petroleum ether, tetrachloroethane, toluene, xylene, and preferably cyclohexane.
The invention relates to a method for modifying the super-dispersibility of rubber filler nano white carbon black. 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. Then unsaturated acrylate and aryl ethylene monomers are subjected to copolymerization reaction to prepare the polar monomer pre-emulsion. The ester group of the polar monomer pre-emulsion and the polar anchor point on the surface of the nano white carbon black particles generate strong mutual attraction between molecules to form a polymer which takes the white carbon black particles as the center and is coated by the organic silicon/alkylphenol polyoxyethylene ether copolymer and the polar monomer pre-emulsion, and then an aryl ethylene monomer is added to carry out copolymerization reaction with the polar monomer emulsion to form an aryl ethylene polymer coating layer on the surface of the nano white carbon black particles.
Because the organic silicon/alkylphenol polyoxyethylene copolymer has a plurality of polar groups, the density of the anchoring points is high, the connection strength is high, the aryl ethylene polymer coating layer is tightly connected with the white carbon black particles, and the separation is difficult to occur even under the action of high temperature and high shear. And the chain structure of the aryl ethylene polymer coating layer has the non-polar characteristic, does not generate the mutual attraction effect, and simultaneously contains a benzene ring structure, so the molecular steric hindrance effect is large. Therefore, under the mutual 'synergistic effect' of the two, a stable space barrier layer can be established between the nano white carbon black particles, the mutual agglomeration of the particles is hindered, and the nano white carbon black particles can exist in a single particle form very stably in the long-term storage and banburying processing processes (see attached figure 1). Meanwhile, the chain structure of the aryl ethylene polymer coating layer is similar to a partial chain segment of the solution-polymerized styrene-butadiene rubber, so that the nano white carbon black particles can be stably and uniformly dispersed in the solution-polymerized styrene-butadiene rubber matrix to achieve ultra-dispersion. The invention has the advantages of low modification cost, small environmental pollution, suitability for industrial production and the like.
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 1705-1680 cm-1A sharp absorption peak of ester group appears, 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 ether copolymer and the polar monomer emulsion containing acrylic ester are 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 following examples and comparative examples are given to illustrate the effects of the present invention, but the scope of the present invention is not limited to these examples and comparative examples. 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
Styrene, 99.5% purity, Laminarian petrochemical company
Dinonylphenol polyoxyethylene ether (DNPEO), Haian Yongsheng chemical Co., Ltd
Dodecyl Polyoxyethylene Ether (DPEO), Haian Yongsheng chemical Co., Ltd
Vinyltrimethoxysilane (A-171), Nanjing chemical Co., Ltd
Vinyltriethoxysilane (A-151), Nanjing chemical Co., Ltd
Methyl Methacrylate (MMA) Guangzhou Qitai chemical Co., Ltd
Potassium persulfate, Hubei Fenxing Galaxy chemical group Co
Other reagents are all commercial products
⑵ analytical test methods:
infrared spectrum analysis of the sample: the functional group analysis is carried out on samples before and after the modification of the nano white carbon black by an infrared spectrometer of German Bruke spectral instrument company. Drying the sample in a vacuum oven at 100 ℃, tabletting by using potassium bromide, and collecting the sample with the wave number range of 400-4000cm-1。
Analyzing a sample by an electron microscope: and (3) carrying out dispersibility analysis on the sample before and after the modification of the nano white carbon black by adopting an XL-20 scanning electron microscope produced by Philips corporation in the Netherlands. And carrying out SEM analysis on the sample under the accelerating voltage of 20kV after the sample is subjected to gold spraying treatment by a surface treatment machine.
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:
wherein ν 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 A-171 and 100 parts of cyclohexane into a reactor, stirring for 1.0hr, then adding 4.0 parts of DNPEO, 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 A-171/DNPEO copolymer a.
(2) Preparing a polar monomer pre-emulsion: placing 100 parts of styrene, 5 parts of MMA, 1.0 part of sodium dodecyl benzene sulfonate and 100 parts of deionized water into a reaction kettle, and stirring and mixing for 10 min; then, 1.0 part of sodium hydroxide and 0.05 part of potassium persulfate were added thereto, and the mixture was heated to 40 ℃ and stirred to react for 1.0hr to prepare a polar monomer pre-emulsion a.
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 5 parts of A-171/DNPEO copolymer a and 200 parts of cyclohexane into a polymerization kettle, heating to 40 ℃, and stirring for reacting for 1.0 hr; then adding 4 parts of polar monomer pre-emulsion a, 200 parts of deionized water, 2 parts of sodium dodecyl benzene sulfonate and 1.0 part of sodium hydroxide, stirring and heating to 70 ℃, and mixing for 30min to generate polymer seeds taking nano white carbon black powder as the center; and finally, adding 20 parts of styrene and 0.1 part of potassium persulfate, reacting for 5.0hr, adding 0.1 part of diethylhydroxylamine, washing, dehydrating, 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 2
(1) Preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 1.
(2) Preparing a polar monomer pre-emulsion: 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 A-171/DNPEO copolymer a and 220 parts of cyclohexane into a polymerization kettle, heating to 42 ℃, and stirring for reacting for 1.3 hours; then adding 5 parts of polar monomer pre-emulsion a, 220 parts of deionized water, 2.5 parts of sodium dodecyl benzene sulfonate and 1.2 parts of sodium hydroxide, stirring and heating to 72 ℃, and mixing for 35min to generate polymer seeds taking nano white carbon black powder as the center; and finally, adding 23 parts of styrene and 0.15 part of potassium persulfate, reacting for 7.0hr, adding 0.2 part of diethylhydroxylamine, washing, dehydrating, 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 a polar monomer pre-emulsion: the same as in example 1.
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 7 parts of A-171/DNPEO copolymer a and 240 parts of cyclohexane into a polymerization kettle, heating to 45 ℃, and stirring for reacting for 1.5 hours; then adding 6 parts of polar monomer pre-emulsion a, 250 parts of deionized water, 3.0 parts of sodium dodecyl benzene sulfonate and 1.5 parts of sodium hydroxide, stirring and heating to 75 ℃, and mixing for 40min to generate polymer seeds taking nano white carbon black powder as the center; and finally, adding 27 parts of styrene and 0.2 part of potassium persulfate, reacting for 7.0hr, adding 0.2 part of diethylhydroxylamine, washing, dehydrating, drying and grinding to obtain the ultra-dispersed nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 4
(1) Preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: adding 100 parts of A-171 and 150 parts of cyclohexane into a reactor, stirring for 1.5 hours, then adding 8.0 parts of DNPEO, continuously stirring and heating until the temperature of the reactor reaches 60 ℃, rapidly adding 1.3 parts of sodium hydroxide under the stirring condition, reacting for 8.0 hours, and then decompressing and distilling to obtain an A-171/DNPEO copolymer b.
(2) Preparing a polar monomer pre-emulsion: placing 100 parts of styrene, 8 parts of MMA, 3 parts of sodium dodecyl benzene sulfonate and 150 parts of deionized water into a reaction kettle, and stirring and mixing for 20 min; then, 1.5 parts of sodium hydroxide and 0.13 part of potassium persulfate were added thereto, and the mixture was heated to 50 ℃ and stirred to react for 2.0hr to prepare a polar monomer pre-emulsion b.
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 8 parts of A-171/DNPEO copolymer b and 260 parts of cyclohexane into a polymerization kettle, heating to 47 ℃, and stirring for reacting for 1.8 hours; then adding 7 parts of polar monomer pre-emulsion b, 270 parts of deionized water, 4.0 parts of sodium dodecyl benzene sulfonate and 1.9 parts of sodium hydroxide, stirring and heating to 75 ℃, and mixing for 45min to generate polymer seeds taking nano white carbon black powder as the center; and finally, adding 30 parts of styrene and 0.3 part of potassium persulfate, reacting for 8.0hr, adding 0.3 part of diethylhydroxylamine, washing, dehydrating, 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 5
(1) Preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 4.
(2) Preparing a polar monomer pre-emulsion: the same as in example 4.
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 9 parts of A-171/DNPEO copolymer b and 280 parts of cyclohexane into a polymerization kettle, heating to 50 ℃, and stirring for reacting for 2.0 hr; then adding 8 parts of polar monomer pre-emulsion b, 270 parts of deionized water, 4.0 parts of sodium dodecyl benzene sulfonate and 2.0 parts of sodium hydroxide, stirring and heating to 75 ℃, and mixing for 45min to generate polymer seeds taking nano white carbon black powder as the center; and finally, adding 33 parts of styrene and 0.35 part of potassium persulfate, reacting for 8.5 hours, adding 0.3 part of diethylhydroxylamine, and washing, dehydrating, 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 a polar monomer pre-emulsion: the same as in example 4.
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 10 parts of A-171/DNPEO copolymer b and 300 parts of cyclohexane into a polymerization kettle, heating to 52 ℃, and stirring for reacting for 2.2 hours; then adding 9 parts of polar monomer pre-emulsion b, 270 parts of deionized water, 4.5 parts of sodium dodecyl benzene sulfonate and 2.2 parts of sodium hydroxide, stirring and heating to 75 ℃, and mixing for 45min to generate polymer seeds taking nano white carbon black powder as the center; and finally, adding 35 parts of styrene and 0.4 part of potassium persulfate, reacting for 8.5 hours, adding 0.3 part of diethylhydroxylamine, and washing, dehydrating, 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 13 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 a polar monomer pre-emulsion: placing 100 parts of styrene, 10 parts of MMA, 5 parts of sodium dodecyl benzene sulfonate and 200 parts of deionized water into a reaction kettle, and stirring and mixing for 30 min; then, 2.0 parts of sodium hydroxide and 0.2 part of potassium persulfate were added, and the mixture was heated to 60 ℃ and stirred to react for 3.0hr to prepare a polar monomer pre-emulsion c.
(3) Preparing the ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 12 parts of A-151/DPEO copolymer c and 350 parts of cyclohexane into a polymerization kettle, heating to 55 ℃, and stirring for reaction for 2.0 hr; then adding 10 parts of polar monomer pre-emulsion c, 280 parts of deionized water, 5.0 parts of sodium dodecyl benzene sulfonate and 2.3 parts of sodium hydroxide, stirring and heating to 78 ℃, and mixing for 47min to generate polymer seeds taking nano white carbon black powder as the center; and finally, adding 37 parts of styrene and 0.4 part of potassium persulfate, reacting for 9.0hr, adding 0.4 part of diethylhydroxylamine, washing, dehydrating, 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 a polar monomer pre-emulsion: 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 350 parts of cyclohexane into a polymerization kettle, heating to 55 ℃, and stirring for reaction for 2.5 hours; then adding 11 parts of polar monomer pre-emulsion c, 290 parts of deionized water, 5.5 parts of sodium dodecyl benzene sulfonate and 2.5 parts of sodium hydroxide, stirring and heating to 78 ℃, and mixing for 48min to generate polymer seeds taking nano white carbon black powder as the center; and finally adding 39 parts of styrene and 0.45 part of potassium persulfate, reacting for 9.0hr, adding 0.4 part of diethylhydroxylamine, washing, dehydrating, 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 a polar monomer pre-emulsion: 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 12 parts of polar monomer pre-emulsion c, 300 parts of deionized water, 6.0 parts of sodium dodecyl benzene sulfonate and 3.0 parts of sodium hydroxide, stirring and heating to 80 ℃, and mixing for 50min to generate polymer seeds taking nano white carbon black powder as the center; and finally, adding 40 parts of styrene and 0.5 part of potassium persulfate, reacting for 10 hours, adding 0.5 part of diethylhydroxylamine, washing, dehydrating, 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 a polar monomer pre-emulsion: 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 the A-171/DNPEO copolymer a added during the preparation was 4.0 parts, namely: adding 100 parts of nano white carbon black (40nm), 4.0 parts of A-171/DNPEO copolymer a and 200 parts of cyclohexane into a polymerization kettle, heating to 40 ℃, and stirring for reacting for 1.0 hr; then adding 4 parts of polar monomer pre-emulsion a, 200 parts of deionized water, 2 parts of sodium dodecyl benzene sulfonate and 1.0 part of sodium hydroxide, stirring and heating to 70 ℃, and mixing for 30min to generate polymer seeds taking nano white carbon black powder as the center; and finally, adding 20 parts of styrene and 0.1 part of potassium persulfate, reacting for 5.0hr, adding 0.1 part of diethylhydroxylamine, washing, dehydrating, 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 2
(1) Preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 2.
(2) Preparing a polar monomer pre-emulsion: the same as in example 2.
(3) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 2 except that the amount of the polar monomer pre-emulsion a added during the preparation was 3.0 parts, that is: adding 100 parts of nano white carbon black (40nm), 6 parts of A-171/DNPEO copolymer a and 220 parts of cyclohexane into a polymerization kettle, heating to 42 ℃, and stirring for reacting for 1.3 hours; then adding 3.0 parts of polar monomer pre-emulsion a, 220 parts of deionized water, 2.5 parts of sodium dodecyl benzene sulfonate and 1.2 parts of sodium hydroxide, stirring and heating to 72 ℃, and mixing for 35min to generate polymer seeds taking nano white carbon black powder as the center; and finally, adding 23 parts of styrene and 0.15 part of potassium persulfate, reacting for 7.0hr, adding 0.2 part of diethylhydroxylamine, washing, dehydrating, 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 a polar monomer pre-emulsion: 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 A-171/DNPEO copolymer a was not added during the preparation, but A-171 was added directly, namely: adding 100 parts of nano white carbon black (40nm), 7 parts of A-171 and 240 parts of cyclohexane into a polymerization kettle, heating to 45 ℃, and stirring for reacting for 1.5 hours; then adding 6 parts of polar monomer pre-emulsion a, 250 parts of deionized water, 3.0 parts of sodium dodecyl benzene sulfonate and 1.5 parts of sodium hydroxide, stirring and heating to 75 ℃, and mixing for 40min to generate polymer seeds taking nano white carbon black powder as the center; and finally, adding 27 parts of styrene and 0.2 part of potassium persulfate, reacting for 7.0hr, adding 0.2 part of diethylhydroxylamine, washing, dehydrating, drying and grinding to obtain the ultra-dispersed nano white carbon black. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 4
(1) Preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the other conditions were the same as in example 4 except that the amount of DNPEO added during the preparation was 2.0 parts, that is: adding 100 parts of A-171 and 150 parts of cyclohexane into a reactor, stirring for 1.5 hours, then adding 8.0 parts of DNPEO, continuously stirring and heating until the temperature of the reactor reaches 60 ℃, rapidly adding 1.3 parts of sodium hydroxide under the stirring condition, reacting for 8.0 hours, and then decompressing and distilling to obtain the A-171/DNPEO copolymer b-1.
(2) Preparing a polar monomer pre-emulsion: 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 the A-171/DNPEO copolymer b was not added during the preparation, but the A-171/DNPEO copolymer b-1 was added, namely: adding 100 parts of nano white carbon black (40nm), 8 parts of A-171/DNPEO copolymer b-1 and 260 parts of cyclohexane into a polymerization kettle, heating to 47 ℃, and stirring for reacting for 1.8 hours; then adding 7 parts of polar monomer pre-emulsion b, 270 parts of deionized water, 4.0 parts of sodium dodecyl benzene sulfonate and 1.9 parts of sodium hydroxide, stirring and heating to 75 ℃, and mixing for 45min to generate polymer seeds taking nano white carbon black powder as the center; and finally, adding 30 parts of styrene and 0.3 part of potassium persulfate, reacting for 8.0hr, adding 0.3 part of diethylhydroxylamine, washing, dehydrating, 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 5
(1) Preparing a polar monomer pre-emulsion: 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 A-171/DNPEO copolymer b-1 was not added during the preparation, but DNPEO was added directly, i.e.: adding 100 parts of nano white carbon black (40nm), 9 parts of DNPEO and 280 parts of cyclohexane into a polymerization kettle, heating to 50 ℃, and stirring for reacting for 2.0 hr; then adding 8 parts of polar monomer pre-emulsion b, 270 parts of deionized water, 4.0 parts of sodium dodecyl benzene sulfonate and 2.0 parts of sodium hydroxide, stirring and heating to 75 ℃, and mixing for 45min to generate polymer seeds taking nano white carbon black powder as the center; and finally, adding 33 parts of styrene and 0.35 part of potassium persulfate, reacting for 8.5 hours, adding 0.3 part of diethylhydroxylamine, and washing, dehydrating, 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 a polar monomer pre-emulsion: 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 the A-171/DNPEO copolymer b was not added during the preparation, namely: adding 100 parts of nano white carbon black (40nm) and 300 parts of cyclohexane into a polymerization kettle, heating to 52 ℃, and stirring for reacting for 2.2 hours; then adding 9 parts of polar monomer pre-emulsion b, 270 parts of deionized water, 4.5 parts of sodium dodecyl benzene sulfonate and 2.2 parts of sodium hydroxide, stirring and heating to 75 ℃, and mixing for 45min to generate polymer seeds taking nano white carbon black powder as the center; and finally, adding 35 parts of styrene and 0.4 part of potassium persulfate, reacting for 8.5 hours, adding 0.3 part of diethylhydroxylamine, and washing, dehydrating, 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 a polar monomer pre-emulsion: 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: placing 100 parts of styrene, 4.0 parts of MMA, 5 parts of sodium dodecyl benzene sulfonate and 200 parts of deionized water into a reaction kettle, and stirring and mixing for 30 min; then adding 2.0 parts of sodium hydroxide and 0.2 part of potassium persulfate, heating to 60 ℃, stirring and reacting for 3.0hr to prepare the polar monomer pre-emulsion c-1.
(3) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 7, except that the polar monomer pre-emulsion c was not added during the preparation, but the polar monomer pre-emulsion c-1 was added, namely: adding 100 parts of nano white carbon black (40nm), 12 parts of A-151/DPEO copolymer c and 350 parts of cyclohexane into a polymerization kettle, heating to 55 ℃, and stirring for reaction for 2.0 hr; then adding 10 parts of polar monomer pre-emulsion c-1, 280 parts of deionized water, 5.0 parts of sodium dodecyl benzene sulfonate and 2.3 parts of sodium hydroxide, stirring and heating to 78 ℃, and mixing for 47min to generate polymer seeds taking nano white carbon black powder as the center; and finally, adding 37 parts of styrene and 0.4 part of potassium persulfate, reacting for 9.0hr, adding 0.4 part of diethylhydroxylamine, washing, dehydrating, 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 a polar monomer pre-emulsion: 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 amount of styrene added during the preparation was 10 parts, that is: adding 100 parts of nano white carbon black (40nm), 14 parts of A-151/DPEO copolymer c and 350 parts of cyclohexane into a polymerization kettle, heating to 55 ℃, and stirring for reaction for 2.5 hours; then adding 11 parts of polar monomer pre-emulsion c, 290 parts of deionized water, 5.5 parts of sodium dodecyl benzene sulfonate and 2.5 parts of sodium hydroxide, stirring and heating to 78 ℃, and mixing for 48min to generate polymer seeds taking nano white carbon black powder as the center; and finally, adding 10 parts of styrene and 0.45 part of potassium persulfate, reacting for 9.0hr, adding 0.4 part of diethylhydroxylamine, washing, dehydrating, 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 same as in example 9.
(2) Preparing a polar monomer pre-emulsion: the other conditions were the same as in example 9, except that no MMA was added during the preparation, namely: 100 parts of styrene, 5 parts of sodium dodecyl benzene sulfonate and 200 parts of deionized water are put into a reaction kettle to be stirred and mixed for 30 min; then adding 2.0 parts of sodium hydroxide and 0.2 part of potassium persulfate, heating to 60 ℃, stirring and reacting for 3.0hr to prepare the polar monomer pre-emulsion c-2.
(3) Preparing the ultra-dispersed nano white carbon black: the other conditions were the same as in example 9, except that the polar monomer pre-emulsion c was not added during the preparation, but the polar monomer pre-emulsion c-2 was added, namely: 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 12 parts of polar monomer pre-emulsion c-2, 300 parts of deionized water, 6.0 parts of sodium dodecyl benzene sulfonate and 3.0 parts of sodium hydroxide, stirring and heating to 80 ℃, and mixing for 50min to generate polymer seeds taking nano white carbon black powder as the center; and finally, adding 40 parts of styrene and 0.5 part of potassium persulfate, reacting for 10 hours, adding 0.5 part of diethylhydroxylamine, washing, dehydrating, 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
As can be seen from Table 1: the sedimentation volume ratio of the examples is larger than that of the comparative example at the same time, and the oil absorption is lower than that of the comparative example, which shows that the modification effect of the invention is obvious.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (14)
1. A preparation method of ultra-dispersed nano white carbon black for rubber filler is characterized by comprising the following specific preparation 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 4-13 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 catalyst under the stirring condition, reacting for 5-10 hours, and then decompressing and distilling to obtain organic silicon/alkylphenol polyoxyethylene ether;
(2) preparing a polar monomer pre-emulsion: putting 100 parts by mass of aryl ethylene monomer, 5-10 parts by mass of unsaturated acrylate polar monomer, 1-5 parts by mass of emulsifier and 100-200 parts by mass of deionized water into a reaction kettle, and stirring and mixing for 10-30 min; then adding 1.0-2.0 parts by mass of a buffering agent and 0.05-0.2 part by mass of an initiator, heating to 40-60 ℃, and stirring for reacting for 1-3 hours to prepare a polar monomer pre-emulsion;
(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 4-12 parts by mass of polar monomer pre-emulsion, 200-300 parts by mass of deionized water, 2-6 parts by mass of emulsifier and 1-3 parts by mass of buffering agent, stirring and heating to 70-80 ℃, mixing for 30-50 min to generate a polymer which takes nano white carbon black powder as a center and is coated by organic silicon/alkylphenol polyoxyethylene ether copolymer and polar monomer pre-emulsion, and taking the polymer as a seed; and finally, adding 20-40 parts by mass of aryl ethylene monomer and 0.1-0.5 part by mass of initiator, reacting for 5.0-10 hr, adding 0.1-0.5 part by mass of terminator, washing, dehydrating, 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 selected from the group consisting of nonylphenol ethoxylate, octylphenol ethoxylate, dodecylphenol ethoxylate, and dinonylphenol ethoxylate.
4. The method of claim 3, wherein the alkylphenol ethoxylate is dinonylphenol ethoxylate.
5. The method of claim 1, wherein the silane coupling agent is 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 vinyltrimethoxysilane.
7. The method of claim 1, wherein the catalyst is selected from the group consisting of sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium carbonate, and sodium bicarbonate.
8. The method of claim 7, wherein the catalyst is sodium hydroxide.
9. The method of claim 1, wherein the aryl vinyl compound is one or more of styrene, α -methyl styrene, 2-phenyl styrene, ethyl styrene and their derivatives.
10. The method of claim 9, wherein the aryl vinyl compound is styrene.
11. The method of claim 1, wherein the unsaturated carboxylic acid polar monomer is selected from one or more of methyl methacrylate, ethyl methacrylate, butyl methacrylate and tert-butyl methacrylate.
12. The method of claim 11, wherein the unsaturated carboxylic acid polar monomer is methyl methacrylate.
13. The method of claim 1, wherein the initiator is a water soluble thermal initiator selected from the group consisting of ammonium persulfate, potassium persulfate, and sodium persulfate.
14. The method of claim 13, wherein the initiator is potassium persulfate.
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| CN108192137A (en) * | 2016-12-08 | 2018-06-22 | 中国石油天然气股份有限公司 | It is used as the preparation method of gum filler high dispersive carbon nanotube |
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