CN108192166B - Modification method of high-dispersion rubber filler carbon nano tube - Google Patents

Modification method of high-dispersion rubber filler carbon nano tube Download PDF

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CN108192166B
CN108192166B CN201611123630.3A CN201611123630A CN108192166B CN 108192166 B CN108192166 B CN 108192166B CN 201611123630 A CN201611123630 A CN 201611123630A CN 108192166 B CN108192166 B CN 108192166B
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CN108192166A (en
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徐典宏
李福崇
孟令坤
朱晶
赵洪国
胡海华
李波
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Petrochina Co Ltd
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    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract

The invention aims to provide a method for modifying a rubber filler high-dispersion carbon nano tube. The invention adopts strong oxidizing acid and polyamine to carry out amination treatment on the surface of the carbon nano tube, then adopts unsaturated vinyl amide polar monomer to carry out graft polymerization on solution polymerized styrene-butadiene rubber cement, and finally prepares the high-dispersion carbon nano tube through coating treatment. The method not only solves the problem that the carbon nano tube is easy to agglomerate in the processes of long-term storage and high-temperature and high-shear processing. Meanwhile, the compatibility of the carbon nano tube and the solution polymerized styrene-butadiene rubber is also obviously improved, and the high dispersibility of the carbon nano tube in the solution polymerized styrene-butadiene rubber matrix is endowed.

Description

Modification method of high-dispersion rubber filler carbon nano tube
Technical Field
The invention relates to a preparation method of high dispersibility of a solution polymerized styrene butadiene rubber filler carbon nano tube.
Background
Carbon Nanotubes (CNTs) are a new Carbon structure discovered only in 1991 and are tubes made of graphite sheets formed of Carbon atoms. ByAdopting full SP for carbon atoms in carbon nanotubes2Hybrid linking, compare SP3Hybrid SP2In the hybridization, the S track has more components and the carbon-carbon bond energy is large, so that the carbon nano tube has high modulus and high strength, the tensile strength of the carbon nano tube reaches 50-200 GPa, which is 100 times that of steel, and the density of the carbon nano tube is only 1/6 of steel; the elastic modulus can reach 100TPa, which is equivalent to the elastic modulus of diamond. Therefore, the excellent mechanical properties of the carbon nano tube are more favorable for endowing the polymer material with the characteristics of high strength, low expansion, high wear resistance and the like, and the application prospect in the field of rubber materials is increasingly paid attention to by people. However, since the carbon nanotubes are nano materials, the carbon nanotubes have small particle size, large specific surface area, high surface energy and high tendency to agglomerate, and are easily aggregated into useless lumps in the process of mixing and modifying the rubber material, the problem of uneven dispersion is caused, which not only affects the filling and modifying effect, but also damages the performance of the rubber material.
The research on the carbon nanotube composite modified material has become one of the hot spots in the research field of the current materials. Many methods for modifying carbon nanotubes have been reported in the patent literature. ZL200310109074.0 firstly carries out polarity and non-polarity treatment on the surface of the carbon nano tube to enable the carbon nano tube to have amphipathy, and then carries out surface coating treatment by polyolefin and polyacrylic acid polymers to obtain the carbon nano tube/macromolecule nano composite material. ZL200510009769.0 provides a method for breaking aggregation and entanglement of carbon nanotubes by using dispersion, pulverization, activation and other actions of ultrasonic waves and a high-speed stirring disperser; organic functional groups of the surfactant and the surface of the carbon nano tube are utilized to carry out chemical adsorption or chemical reaction, so that the surfactant covers the surface of the carbon nano tube, and the surface modification and the dispersion of the carbon nano tube in the epoxy resin are realized. ZL200410089036.8 is a carbon nano tube/polyvinyl imidazole nano composite material prepared by taking polyvinyl imidazole as a polymerization monomer and silane, Waran or titanate as a coupling agent through a hydroxylation chemical etching method and a micropulp polymerization method. ZL200410017699.9 is prepared by treating carbon nano-tubes with strong oxidizing acid, reacting with thionyl chloride, and reacting the obtained product with diamine or dihydric alcohol to obtain modified carbon nano-tubes with amino or hydroxyl on the surface; reacting the modified carbon nano tube with amino or hydroxyl on the surface with binary or poly isocyanate to obtain the functionalized carbon nano tube with isocyanate groups on the surface. ZL200310109072.1 processing carbon nanotube to make its surface carry specific initiation group; then, atom transfer radical polymerization is used to initiate the polymerization of the tert-butyl methacrylate monomer, and the tert-butyl methacrylate is hydrolyzed to remove the tert-butyl group and generate carboxyl, thus obtaining the water-soluble carbon nano-tube grafted by the polycarboxy polymer.
Disclosure of Invention
The invention aims to provide a method for modifying high dispersion of rubber filler carbon nanotubes. The invention adopts strong oxidizing acid and polyamine to carry out amination treatment on the surface of the carbon nano tube, then adopts unsaturated vinyl amide polar monomer to carry out graft polymerization on solution polymerized styrene-butadiene rubber cement, and finally prepares the high-dispersion carbon nano tube through coating treatment. The method not only solves the problem that the carbon nano tube is easy to agglomerate in the processes of long-term storage and high-temperature and high-shear processing. Meanwhile, the compatibility of the carbon nano tube and the solution polymerized styrene-butadiene rubber is also obviously improved, and the high dispersibility of the carbon nano tube in the solution polymerized styrene-butadiene rubber matrix is endowed.
The "parts" in the present invention mean parts by mass.
The invention relates to a method for modifying high dispersion of a rubber filler carbon nano tube, which comprises the following specific preparation steps:
(1) preparing carbon nano tube amination: putting 100 parts of carbon nano tube, 150-200 parts of concentrated nitric acid, 50-100 parts of concentrated sulfuric acid and 10-50 parts of potassium permanganate into a reactor together for mixing, treating the mixture with 50-100 kHz ultrasonic waves for 1-2 hours, heating the mixture to 50-90 ℃, stirring and acid boiling the mixture for 1-10 hours, cooling, suction filtering and washing the mixture until filtrate is neutral, finally adding 200-400 parts of polyamine, heating the mixture to 70-90 ℃, stirring and reacting the mixture for 1-5 hours, and performing suction filtering, washing and drying to obtain the carbon nano tube with amino on the surface.
(2) Preparation of graft mucilage: adding 300-600 parts of solvent into a polymerization kettle, sequentially adding 100 parts of solution-polymerized styrene-butadiene rubber cement and 0.05-0.5 part of molecular weight regulator, replacing with nitrogen, adding 1-10 parts of unsaturated vinyl amide polar monomer, stirring, heating, adding 0.05-0.2 part of initiator when the temperature of the polymerization kettle reaches 50-70 ℃, reacting for 1-5 hours, and adding 0.1-0.5 part of terminator to prepare grafted rubber cement (the grafting rate of the solution-polymerized styrene-butadiene rubber cement is 0.3% -1.5%).
(3) Preparing the high-dispersion carbon nano tube: adding 100 parts of aminated carbon nanotube and 300-500 parts of solvent into a polymerization kettle, stirring and mixing for 10-30 min; and then adding 5-20 parts of grafting mucilage, stirring and heating to 50-80 ℃, stirring and reacting for 2-6 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion carbon nano tube.
The carbon nano tube is nano-scale, and the particle size is as follows: 0.3 to 30 nm.
The solution polymerized styrene-butadiene rubber cement is prepared by the solution polymerization copolymerization of a conjugated diene compound and an aryl ethylene compound. Wherein the solid content of the solution polymerized styrene-butadiene rubber cement is 5-20 w%.
The polyamine in the invention is selected from one of ethylenediamine, triethylamine, diethylenetriamine, hexamethylenetetramine and isophoronediamine, and hexamethylenetetramine is preferred.
The vinyl amide polar monomer is selected from one or a mixture of more of acrylamide, methacrylamide, 1-butene amide, methacrylamide and 1-hexene amide, and preferably methacrylamide.
The initiator is selected from one of dicumyl peroxide, cumene hydroperoxide, dibenzoyl peroxide and di-tert-butyl peroxide, and is preferably dicumyl peroxide (DCP).
The solvent of the invention is selected from cyclohexane and carbon disulfide (CS)2) Nitrobenzene, petroleum ether, tetrachloroethane, toluene, xylene, and preferably cyclohexane.
The molecular weight regulator is selected from one of tertiary dodecyl mercaptan, tertiary tetradecyl mercaptan and tertiary hexadecyl mercaptan, and the tertiary dodecyl mercaptan is preferred.
The terminating agent is selected from one of diethylhydroxylamine, hydroxylamine sulfate and sodium dimethyl dithiocarbamate, and sodium dimethyl dithiocarbamate is preferred.
The invention relates to a method for modifying a carbon nano tube used as a rubber filler, which comprises the steps of firstly carrying out amination treatment on the surface of the carbon nano tube by adopting strong oxidizing acid and polyamine to ensure that the surface of the carbon nano tube has amino groups, and because the polyamine contains more amino groups, the carbon nano tube can be adsorbed on the surface of the carbon nano tube in a multi-point anchoring mode. The amine group of the anchoring point and the polar group amide group of the grafted solution-polymerized styrene-butadiene rubber cement generate mutual attraction among molecules, and a coating layer of the solution-polymerized styrene-butadiene rubber cement is formed on the surface of the carbon nano tube particle. The chain structure of the coating layer has the non-polar characteristic, the mutual attraction effect is avoided, and the coating layer also contains a benzene ring structure, so that the molecular steric hindrance effect is large; in addition, the coating layer is adsorbed on the surface of the carbon nano tube in a multi-point anchoring mode, and has enough adsorption strength. Therefore, under the mutual 'synergistic effect' of the two, the carbon nano tube coated by the solution polymerized styrene-butadiene rubber cement can stably exist in a single particle form during long-term storage and high-temperature and high-shear processing. Therefore, the problem that the carbon nano tube is easy to agglomerate is solved, the compatibility with the solution polymerized styrene butadiene rubber can be obviously improved, and the carbon nano tube can be stably and uniformly dispersed in a solution polymerized styrene butadiene rubber matrix. The invention has the advantages of small environmental pollution, suitability for industrial production and the like.
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FIG. 1 shows the IR spectra of carbon nanotube (a) and highly dispersed carbon nanotube (b). As can be seen from the figure: FTIR spectrum of sample b at wavenumber 3100cm-1And 3150cm-1The characteristic absorption peak of the ethylene aryl appears; at a wave number of 1650cm-1And 1680cm-1The amide group sharp absorption peak appears; at wave number of 1715cm-1The absorption peak at (A) is a characteristic absorption peak of the ester group. Where the FTIR spectrum of sample a shows no absorption peaks. The result shows that the graft polymer of the unsaturated vinyl amide polar monomer and the solution polymerized styrene-butadiene rubber cement is deposited on the surface of the carbon nano tube particle.
Detailed Description
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.
Firstly, raw material sources:
Figure GDA0002295387140000041
the method comprises the following steps:
determination of the graft ratio: taking about 4g of sample from a three-necked bottle by using a pipette, weighing, adding 2-3 drops of hydroquinone solution, drying to constant weight, putting the sample in a Soxhlet fat extractor, extracting and extracting for 24 hours by using toluene in a water bath at 90 ℃, and drying to constant weight. The monomer grafting was calculated as follows:
Figure GDA0002295387140000042
in the formula: m is0-total mass of cement (g); m-sample mass (g) weighed after reaction; m ism-total mass of monomers in the reactants (g); m isSBR-mass of styrene butadiene rubber in the sample (g); m is1-mass of sample after extraction (g).
Infrared spectrum analysis of the sample: and (3) performing functional group analysis on the samples before and after the modification of the carbon nano tube by adopting 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 wave number range of 400-4000 cm—1。
The method for measuring the sedimentation volume comprises the following steps: weighing 10g of high-dispersion carbon nano tube, placing the high-dispersion carbon nano tube in a graduated 100mL measuring cylinder with a plug, adding a certain amount of dispersing agent (liquid paraffin), adding the liquid paraffin to the 100mL scale after the high-dispersion carbon nano tube is completely soaked by the liquid paraffin, fully oscillating for 5min at the oscillation frequency of 30 times/1 min to ensure that the high-dispersion carbon nano tube 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, which indicates that the carbon nano tube is good in dispersion and easy to be compatible.
Method for measuring oil absorption: referring to YS/T618-2007 method for measuring oil absorption of aluminum hydroxide for filler, a quantitative high-dispersion carbon nano tube is put into a watch glass, diisooctyl phthalate is dripped by 0.2mL of dioctyl phthalate, after each dripping, the mixture is fully ground by a knife until the powder can be bonded into large clusters without cracking, and the oil absorption is V of the volume absorbed by each 100g of sample0(mL) as follows:
Figure GDA0002295387140000051
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 highly dispersed carbon nanotubes to some extent, the lower the specific surface area, the lower the oil absorption and the better the wettability, and vice versa.
Example 1
(1) Preparing carbon nano tube amination: mixing 100 parts of carbon nano tube, 150 parts of concentrated nitric acid, 50 parts of concentrated sulfuric acid and 10 parts of potassium permanganate in a reactor, treating the mixture for 1 hour by using 50kHz ultrasonic wave, heating the mixture to 50 ℃, stirring and acid boiling the mixture for 2 hours, cooling, carrying out suction filtration and washing until the filtrate is neutral, finally adding 200 parts of hexamethylenetetramine, heating the mixture to 70 ℃, carrying out stirring reaction for 2 hours, carrying out suction filtration, washing and drying to obtain the carbon nano tube a with amino on the surface.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: adding 300 parts of cyclohexane into a polymerization kettle, then sequentially adding 100 parts of solution-polymerized styrene-butadiene rubber cement SSBR2564s and 0.05 part of tert-dodecyl mercaptan, replacing with nitrogen, adding 1 part of methacrylamide, stirring, heating, adding 0.05 part of DCP when the temperature of the polymerization kettle reaches 50 ℃, reacting for 1hr, and adding 0.1 part of sodium ferbamate to prepare the graft solution-polymerized styrene-butadiene rubber cement a (the grafting rate is 0.4%).
(3) Preparing the high-dispersion carbon nano tube: adding 100 parts of aminated carbon nanotube a and 300 parts of cyclohexane into a polymerization kettle, and stirring and mixing for 10 min; then adding 5 parts of graft solution polymerized styrene-butadiene rubber cement a, stirring and heating to 50 ℃, stirring and reacting for 2 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion carbon nano tube. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 2
(1) Preparing carbon nano tube amination: the same as in example 1.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 1.
(3) Preparing the high-dispersion carbon nano tube: adding 100 parts of aminated carbon nanotube a and 350 parts of cyclohexane into a polymerization kettle, stirring and mixing for 15 min; then 8 parts of graft solution polymerized styrene-butadiene rubber cement a is added, stirred and heated to 60 ℃, stirred and reacted for 3 hours, and then the high-dispersion carbon nano tube 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 3
(1) Preparing carbon nano tube amination: mixing 100 parts of carbon nano tube, 180 parts of concentrated nitric acid, 70 parts of concentrated sulfuric acid and 30 parts of potassium permanganate in a reactor, treating the mixture for 1.5 hours by using 80kHz ultrasonic wave, heating the mixture to 70 ℃, stirring and acid boiling the mixture for 5 hours, cooling, carrying out suction filtration and washing until the filtrate is neutral, finally adding 300 parts of hexamethylenetetramine, heating the mixture to 80 ℃, stirring and reacting for 3 hours, carrying out suction filtration, washing and drying to obtain the carbon nano tube b with amino on the surface.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: adding 450 parts of cyclohexane into a polymerization kettle, then sequentially adding 100 parts of solution-polymerized styrene-butadiene rubber cement SSBR2564s and 0.3 part of tert-dodecyl mercaptan, replacing with nitrogen, adding 7 parts of methacrylamide, stirring, heating, adding 0.1 part of DCP when the temperature of the polymerization kettle reaches 60 ℃, reacting for 3 hours, and adding 0.3 part of sodium ferbamate to prepare grafted solution-polymerized styrene-butadiene rubber cement b (the grafting rate is 1.1%).
(3) Preparing the high-dispersion carbon nano tube: adding 100 parts of aminated carbon nanotube b and 400 parts of cyclohexane into a polymerization kettle, and stirring and mixing for 20 min; then 10 parts of graft solution polymerized styrene-butadiene rubber cement b is added, stirred and heated to 65 ℃, stirred and reacted for 4 hours, and then the high-dispersion carbon nano tube 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 carbon nano tube amination: the same as in example 3.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 3.
(3) Preparing the high-dispersion carbon nano tube: adding 100 parts of aminated carbon nanotube b and 450 parts of cyclohexane into a polymerization kettle, and stirring and mixing for 20 min; then adding 13 parts of graft solution polymerized styrene-butadiene rubber cement b, stirring and heating to 65 ℃, stirring and reacting for 4 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion carbon nano tube. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 5
(1) Preparing carbon nano tube amination: the same as in example 3.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 3.
(3) Preparing the high-dispersion carbon nano tube: adding 100 parts of aminated carbon nanotube b and 450 parts of cyclohexane into a polymerization kettle, and stirring and mixing for 25 min; then adding 15 parts of grafted solution polymerized styrene-butadiene rubber cement b, stirring and heating to 65 ℃, stirring and reacting for 4 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion carbon nano tube. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 6
(1) Preparing carbon nano tube amination: mixing 100 parts of carbon nano tube with 200 parts of concentrated nitric acid, 100 parts of concentrated sulfuric acid and 50 parts of potassium permanganate in a reactor, treating the mixture for 2 hours by using 100kHz ultrasonic waves, heating the mixture to 90 ℃, stirring and boiling the mixture for 10 hours, cooling, carrying out suction filtration and washing until the filtrate is neutral, finally adding 400 parts of diethylenetriamine, heating the mixture to 90 ℃, stirring and reacting for 5 hours, carrying out suction filtration, washing and drying to obtain the carbon nano tube c with amino groups on the surface.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: adding 600 parts of cyclohexane into a polymerization kettle, then sequentially adding 100 parts of solution-polymerized styrene-butadiene rubber cement SSBR2564s and 0.5 part of tert-dodecyl mercaptan, replacing with nitrogen, adding 10 parts of methacrylamide, stirring, heating, adding 0.2 part of DCP when the temperature of the polymerization kettle reaches 70 ℃, reacting for 10 hours, and adding 0.5 part of sodium ferbamate to prepare grafted solution-polymerized styrene-butadiene rubber cement c (the grafting rate is 1.4%).
(3) Preparing the high-dispersion carbon nano tube: adding 100 parts of aminated carbon nanotube c and 480 parts of cyclohexane into a polymerization kettle, and stirring and mixing for 25 min; then adding 18 parts of graft solution polymerized styrene-butadiene rubber cement c, stirring and heating to 75 ℃, stirring and reacting for 5 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion carbon nano tube. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 7
(1) Preparing carbon nano tube amination: the same as in example 6.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 6.
(3) Preparing the high-dispersion carbon nano tube: adding 100 parts of aminated carbon nanotube c and 500 parts of cyclohexane into a polymerization kettle, stirring and mixing for 30 min; then 20 parts of graft solution polymerized styrene-butadiene rubber cement c is added, stirred and heated to 80 ℃, stirred and reacted for 6 hours, and then the high-dispersion carbon nano tube is prepared by flash evaporation, drying and grinding. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 1
(1) Preparing carbon nano tube amination: the same as in example 1.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 1.
(3) Preparing the high-dispersion carbon nano tube: the other conditions are the same as example 1, except that the addition amount of the graft solution polymerized styrene-butadiene rubber cement a in the preparation process is 2 parts, namely: adding 100 parts of aminated carbon nanotube a and 300 parts of cyclohexane into a polymerization kettle, and stirring and mixing for 10 min; then adding 2 parts of graft solution polymerized styrene-butadiene rubber cement a, stirring and heating to 50 ℃, stirring and reacting for 2 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion carbon nano tube. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 2
(1) Preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 1.
(2) Preparing the high-dispersion carbon nano tube: the other conditions were the same as in example 2, except that the aminated carbon nanotube a was not added in the preparation process, but the non-aminated carbon nanotube was directly added, that is: adding 100 parts of carbon nano tube and 350 parts of cyclohexane into a polymerization kettle, stirring and mixing for 15 min; then 8 parts of graft solution polymerized styrene-butadiene rubber cement a is added, stirred and heated to 60 ℃, stirred and reacted for 3 hours, and then the high-dispersion carbon nano tube 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 3
(1) Preparing carbon nano tube amination: the same as in example 3.
(2) Preparing the high-dispersion carbon nano tube: the other conditions were the same as in example 3, except that the graft solution-polymerized styrene-butadiene rubber cement b was not added in the preparation process, that is: and (3) adding 100 parts of aminated carbon nanotube b and 400 parts of cyclohexane into a polymerization kettle, stirring and mixing for 20min, and carrying out flash evaporation, drying and grinding to obtain the high-dispersion carbon nanotube. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 4
(1) Preparing carbon nano tube amination: the same as in example 3.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: the same as in example 3.
(3) Preparing the high-dispersion carbon nano tube: the other conditions are the same as example 4, except that the addition amount of the graft solution polymerized styrene-butadiene rubber cement b in the preparation process is 4.5 parts, namely: adding 100 parts of aminated carbon nanotube b and 450 parts of cyclohexane into a polymerization kettle, and stirring and mixing for 20 min; then 4.5 parts of graft solution polymerized styrene-butadiene rubber cement b is added, stirred and heated to 65 ℃, stirred and reacted for 4 hours, and then flash evaporation, drying and grinding are carried out to obtain the high-dispersion carbon nano tube. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 5
(1) Preparing carbon nano tube amination: the same as in example 3.
(2) Preparing the high-dispersion carbon nano tube: the other conditions were the same as in example 5, except that the solution-polymerized styrene-butadiene rubber cement SSBR2564s was added instead of the graft solution-polymerized styrene-butadiene rubber cement b during the preparation, namely: adding 100 parts of aminated carbon nanotube b and 450 parts of cyclohexane into a polymerization kettle, and stirring and mixing for 25 min; then adding 15 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s, stirring and heating to 65 ℃, stirring and reacting for 4 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion carbon nano tube. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 6
(1) Preparing carbon nano tube amination: the same as in example 6.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: the other conditions were the same as in example 6 except that 0.5 part of methacrylamide was added in the preparation, namely: adding 600 parts of cyclohexane into a polymerization kettle, then sequentially adding 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s and 0.5 part of tert-dodecyl mercaptan, replacing with nitrogen, adding 0.5 part of methacrylamide, stirring, heating, adding 0.2 part of DCP when the temperature of the polymerization kettle reaches 70 ℃, reacting for 10 hours, and adding 0.5 part of sodium ferbamate to prepare grafted solution polymerized styrene-butadiene rubber cement c-1 (the grafting rate is 0.1%).
(3) Preparing the high-dispersion carbon nano tube: the other conditions are the same as example 6, except that the graft solution polymerized styrene-butadiene rubber cement c is not added in the preparation process, but the graft solution polymerized styrene-butadiene rubber cement c-1 is added, namely: adding 100 parts of aminated carbon nanotube c and 480 parts of cyclohexane into a polymerization kettle, and stirring and mixing for 25 min; then adding 18 parts of graft solution polymerized styrene-butadiene rubber cement c-1, stirring and heating to 75 ℃, stirring and reacting for 5 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion carbon nano tube. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 7
(1) Preparing carbon nano tube amination: the same as in example 6.
(2) Preparing graft solution polymerized styrene-butadiene rubber cement: the other conditions were the same as in example 6, except that no DCP was added during the preparation, namely: adding 600 parts of cyclohexane into a polymerization kettle, then sequentially adding 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s and 0.5 part of tert-dodecyl mercaptan, replacing with nitrogen, adding 10 parts of methacrylamide, stirring, heating, reacting for 10 hours when the temperature of the polymerization kettle reaches 70 ℃, and adding 0.5 part of sodium ferulate to prepare the graft solution polymerized styrene-butadiene rubber cement c-2 (the grafting rate is 0.03%).
(3) Preparing the high-dispersion carbon nano tube: the other conditions are the same as example 7, except that the graft solution polymerized styrene-butadiene rubber cement c is not added in the preparation process, but the graft solution polymerized styrene-butadiene rubber cement c-2 is added, namely: adding 100 parts of aminated carbon nanotube c and 500 parts of cyclohexane into a polymerization kettle, stirring and mixing for 30 min; then 20 parts of graft solution polymerized styrene-butadiene rubber cement c-2 is added, stirred and heated to 80 ℃, stirred and reacted for 6 hours, and then flash evaporation, drying and grinding are carried out to obtain the high-dispersion carbon nano tube. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
TABLE 1 sedimentation volume and oil absorption of highly dispersed carbon nanotubes
Figure GDA0002295387140000091
Figure GDA0002295387140000101
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 (15)

1. A method for modifying a high-dispersion rubber filler carbon nanotube is characterized by comprising the following steps:
(1) preparing carbon nano tube amination: putting 100 parts of carbon nano tube, 150-200 parts of concentrated nitric acid, 50-100 parts of concentrated sulfuric acid and 10-50 parts of potassium permanganate into a reactor together by mass parts, mixing, treating with 50-100 kHz ultrasonic waves for 1-2 hours, heating to 50-90 ℃, stirring, acid boiling for 1-10 hours, cooling, suction filtering and washing until filtrate is neutral, finally adding 200-400 parts of polyamine, heating to 70-90 ℃, stirring and reacting for 1-5 hours, suction filtering, washing and drying to obtain the carbon nano tube with amino on the surface;
(2) preparation of graft mucilage: according to the mass parts, firstly adding 300-600 parts of solvent into a polymerization kettle, then sequentially adding 100 parts of solution-polymerized styrene-butadiene rubber cement and 0.05-0.5 part of molecular weight regulator, replacing with nitrogen, adding 1-10 parts of unsaturated vinyl amide polar monomer, stirring and heating, adding 0.05-0.2 part of initiator when the temperature of the polymerization kettle reaches 50-70 ℃, reacting for 1-5 hours, and adding 0.1-0.5 part of terminator to prepare grafted rubber cement;
(3) preparing the high-dispersion carbon nano tube: adding 100 parts by mass of aminated carbon nanotube and 300-500 parts by mass of solvent into a polymerization kettle, and stirring and mixing for 10-30 min; and then adding 5-20 parts of grafting mucilage, stirring and heating to 50-80 ℃, stirring and reacting for 2-6 hours, and then carrying out flash evaporation, drying and grinding to obtain the high-dispersion carbon nano tube.
2. The method of claim 1, wherein the carbon nanotubes are nanoscale and have a particle size of 0.3 to 30 nm.
3. The method according to claim 1 or 2, wherein the polyamine is selected from one of ethylenediamine, triethylamine, diethylenetriamine, hexamethylenetetramine and isophoronediamine.
4. The method of claim 3, wherein the polyamine is hexamethylenetetramine.
5. The method of claim 1 or 2, wherein the solution-polymerized styrene-butadiene rubber cement is prepared by solution polymerization copolymerization of a conjugated diene compound and an aryl ethylene compound, wherein the solid content of the solution-polymerized styrene-butadiene rubber cement is 5-20 w%.
6. The method according to claim 1 or 2, wherein the vinyl amide polar monomer is one or more selected from acrylamide, methacrylamide, 1-butenamide, methacrylamide and 1-hexenamide.
7. The method of claim 6, wherein the vinyl amide polar monomer is methacrylamide.
8. The method of claim 1 or 2, wherein the initiator is selected from one of dicumyl peroxide, cumene hydroperoxide, dibenzoyl peroxide and di-t-butyl peroxide.
9. The method of claim 8, wherein the initiator is dicumyl peroxide.
10. The method of claim 1 or 2, wherein the solvent is selected from one of cyclohexane, carbon disulfide, nitrobenzene, petroleum ether, tetrachloroethane, toluene, xylene.
11. The method of claim 10, wherein the solvent is cyclohexane.
12. The method of claim 1 or 2, wherein the molecular weight regulator is selected from one of tertiary decamercaptan, tertiary dodecanethiol, tertiary tetradecanethiol, and tertiary hexadecanethiol.
13. The method of claim 12, wherein the molecular weight regulator is t-dodecyl mercaptan.
14. The method of claim 1 or 2, wherein the terminating agent is selected from one of diethylhydroxylamine, hydroxylamine sulfate, and sodium fermet.
15. The method of claim 14, wherein the terminating agent is sodium fermet.
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