CN115028906A - Preparation method of high-dispersion carbon nano composite masterbatch - Google Patents

Preparation method of high-dispersion carbon nano composite masterbatch Download PDF

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CN115028906A
CN115028906A CN202210496169.5A CN202210496169A CN115028906A CN 115028906 A CN115028906 A CN 115028906A CN 202210496169 A CN202210496169 A CN 202210496169A CN 115028906 A CN115028906 A CN 115028906A
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carbon nano
carbon
composite
dispersion
nano tube
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王海燕
邵光谱
邵路
王宏
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Qingdao Black Cat New Material Research Institute Co ltd
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Qingdao Black Cat New Material Research Institute Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2407/00—Characterised by the use of natural rubber
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • 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
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Abstract

The invention relates to the technical field of rubber masterbatch preparation, in particular to a preparation method of high-dispersion carbon nano composite masterbatch, which comprises the steps of shearing carbon nano tubes in dispersion liquid to prepare short-cut carbon nano tube suspension; introducing an oxidizing gas to oxidize the short carbon tube suspension to prepare a short carbon nanotube oxidizing solution; adding the reinforcing material into the short-cut carbon nanotube oxidizing solution to prepare carbon nanotube slurry; adding a coupling agent into the carbon nano tube slurry to prepare composite slurry; dispersing natural rubber latex into the composite slurry to prepare the carbon nano tube-natural rubber composite material; and solidifying and drying the carbon nano tube-natural rubber composite material to obtain the high-dispersion carbon nano composite master batch. On the basis of uniform dispersion of the carbon nano-tubes, functional groups such as carboxyl, hydroxyl and the like are introduced on the surfaces of the carbon nano-tubes, so that the entanglement and agglomeration phenomenon among the carbon nano-tubes is weakened, the reactivity of the carbon nano-tubes combined with other substances is increased, and the coupling reaction of a coupling agent and oxygen-containing functional groups on the surfaces of the carbon nano-tubes can be realized to improve the dispersion of the carbon nano-tubes in latex.

Description

Preparation method of high-dispersion carbon nano composite masterbatch
Technical Field
The invention relates to the technical field of rubber master batch preparation, in particular to a preparation method of a high-dispersion carbon nano composite master batch.
Background
Carbon nanotubes are one-dimensional nanomaterials, and in the field of engineering materials, carbon nanotubes are ideal fillers for polymer materials due to excellent physical and mechanical properties of the carbon nanotubes. The carbon nano tube has excellent mechanical property, electric conduction and heat conduction performance, so the carbon nano tube is considered to be an ideal mechanical strengthening and functional modifying material of a polymer matrix composite, the composite made of the carbon nano tube has good strength, elasticity and fatigue resistance, and the carbon nano tube is gradually used in the industries of rubber products, tires, plastics and the like.
However, the carbon nanotubes are in a nanofiber shape, are easy to agglomerate and tangle, have a regular graphite wafer structure on the surface, have high surface inertness and poor affinity with a polymer matrix, and therefore, the carbon nanotubes have poor dispersibility in a rubber matrix and high cost, which limits the large-scale application of the carbon nanotubes in rubber.
In the rubber industry, filling carbon nanotubes into various rubber substrates to improve the performance of the rubber substrates becomes one of ideal blending composite materials for researching high-end rubber products, but the carbon nanotubes have high surface free energy and are easy to agglomerate, the interaction between the carbon nanotubes and the substrates is another difficult problem, the surfaces of the carbon nanotubes do not have any reaction functional diagram, the inertia of the carbon nanotubes makes the chemical interface between the carbon nanotubes and the polymer substrates weak, and the improvement effect of the carbon nanotubes on the polymer substrates is difficult to achieve the expectation, so that the carbon nanotubes and the composite materials thereof with uniform size, good dispersion and stable performance are prepared, and the requirements for expanding the application field of the carbon nanotubes and the composite materials thereof are needed.
At present, many advances have been made in the study of the dispersibility of carbon tubes and their composites. The most common method is to modify the surface of the carbon tube by adopting a surfactant, and compound the suspension and latex to prepare the composite masterbatch, the technology solves the dispersion of the carbon nanotube to a certain extent, but the performance of the composite masterbatch is reduced due to the addition of other groups in the surfactant; therefore, it is necessary to provide a technical solution to avoid the influence of the addition of the active agent on the bonding between the carbon nanotubes and the polymer.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a high-dispersion carbon nano composite masterbatch, which introduces functional groups such as carboxyl, hydroxyl and the like on the surface of a carbon nano tube on the basis of uniform dispersion of the carbon nano tube and avoids the influence of the addition of a coupling agent on the combination between the carbon nano tube and latex.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a preparation method of high-dispersion carbon nano composite masterbatch comprises the following steps:
s1, shearing the carbon nano tubes in the dispersion liquid to prepare a chopped carbon nano tube suspension;
s2, introducing an oxidizing gas to oxidize the short carbon tube suspension to obtain a short carbon nanotube oxidizing solution;
s3, adding the reinforcing material into the short-cut carbon nanotube oxidizing solution to prepare carbon nanotube slurry;
s4, adding a coupling agent into the carbon nano tube slurry to prepare composite slurry;
s5, dispersing the natural rubber latex into the composite slurry to prepare the carbon nano tube-natural rubber composite material;
s6, solidifying and drying the carbon nano tube-natural rubber composite material to obtain the high-dispersion carbon nano composite masterbatch.
According to one embodiment of the invention, the dispersion is water; the mass ratio of the carbon nano tube to the water is 1: 20-1: 200.
According to one embodiment of the invention, the length of the carbon nanotubes in the chopped carbon nanotube oxidation solution is 50 nm-50 μm.
According to an embodiment of the present invention, the oxidizing gas in step S2 is one of oxygen, ozone, fluorine, chlorine, and nitrogen dioxide.
According to an embodiment of the invention, the oxidation reaction temperature in the step S2 is 5-40 ℃, and the oxidation time is 20-120 min.
According to an embodiment of the present invention, the oxidation is performed in the oxidation circulation system in step S2, and the reaction temperature in the oxidation circulation system is controlled by a water cooling system; wherein oxidation circulation system can realize the abundant contact of liquid with gaseous, and water cooling system discharges in time and cools down to the heat that the raw materials reaction of oxidation circulation system inside produced.
According to one embodiment of the invention, the reinforcing material in step S3 is carbon black or silica; wherein the carbon black is carbon black for rubber, such as carbon black N115, N234; the nitrogen adsorption specific surface area of the silicon dioxide is 100m 2 /g~200m 2 /g。
According to one embodiment of the invention, the mass ratio of the reinforcing material to the oxidation liquid of the carbon nanotubes is 1:10 to 1: 50.
According to an embodiment of the invention, the reinforcing material is added with the chopped carbon nanotube oxidation solution in the step S3, and then stirred and mixed, wherein the stirring time is 30min to 250 min.
According to one embodiment of the present invention, the stirring in step S3 employs a parallel type stirring blade.
According to an embodiment of the present invention, the coupling agent in step S4 is one of a silane coupling agent, an amino borate, and a silicon boron coupling agent.
According to an embodiment of the present invention, the silane coupling agent is one of a sulfur-containing silane coupling agent, a vinyl silane coupling agent, an epoxy silane coupling agent, (meth) acryloyloxy silane coupling agent, an isocyanate-containing silane coupling agent, a long-chain alkyl silane coupling agent, and an unsaturated coupling agent.
According to one embodiment of the invention, the addition amount of the coupling agent accounts for 0.5-8% of the total mass of the reinforcing material.
According to an embodiment of the present invention, the natural rubber in step S5 is one of hevea rubber latex, prevulcanized natural rubber latex, concentrated natural rubber latex having a solid content of 60%, and prevulcanized concentrated natural rubber latex.
According to an embodiment of the invention, the dispersing in the step S5 is specifically that the composite slurry is sprayed by a high-pressure pump to be mixed with the natural rubber latex and uniformly dispersed by stirring; the stirring speed is 400 r.min -1 。
According to an embodiment of the invention, the solidification in step S6 is carried out by water bath solidification at a temperature of 40-70 ℃.
According to an embodiment of the invention, the drying in the step S6 is specifically vacuum drying at 60 ℃ for 6-12 h.
According to an embodiment of the present invention, the mass ratio of the addition amount of the natural rubber latex to the reinforcing filler in step S6 is 2: 1-5: 1.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the high-dispersion carbon nano composite masterbatch provided by the invention, functional groups such as carboxyl, hydroxyl and the like are introduced on the surface of the carbon nano tube on the basis of uniform dispersion of the carbon nano tube, and compared with other modification methods, the method avoids introducing other functional groups to influence the binding capacity between the carbon tube and the polymer.
2. The carbon tubes in the carbon nanotube dispersion liquid obtained by shearing and dispersing are uniform in size and free from winding and agglomeration.
3. Through oxidation, the surface of the oxidized carbon nano tube contains a certain amount of oxygen-containing groups such as carboxyl, hydroxyl and the like, so that the entanglement and agglomeration phenomenon among the carbon tubes is weakened, and the reactivity of the carbon nano tube combined with other substances is increased. The oxidizing gas is in contact oxidation with the liquid-phase carbon nano tube, so that dust flying in the process of gas-phase oxidation of the carbon nano tube is avoided, the formation of heat in the oxidation reaction is reduced, the oxidation effect on the carbon nano tube can be improved, the oxidation time is shortened, and the dispersion of the carbon nano tube is improved. The reaction temperature of the oxidation is controlled to be 5-40 ℃, and the decomposition of the oxidation gas at a higher temperature is avoided.
4. The carbon black or the silicon dioxide is used as the reinforcing agent, the oxidizing liquid added into the carbon nano tube can realize the full mixing of the carbon black and the carbon tube only by high-speed stirring, the structural performance of the carbon black or the silicon dioxide is prevented from being damaged by ball milling, and the reinforcing effect is enhanced.
5. The carbon nano tube and the carbon black are functionalized and modified by the coupling agent, so that the coupling agent is hydrolyzed in slurry and then is subjected to coupling reaction with oxygen-containing functional groups (such as hydroxyl groups and the like) on the surface of the carbon material to produce hydrogen bonds or dehydrate into ether bonds, the distance between the carbon materials is increased, the agglomeration tendency between the carbon materials is weakened, the modified nano carbon material slurry can more easily enter rubber macromolecules, so that the substances are more uniformly interspersed and dispersed, and a mixture of the carbon nano tube as a bridge to connect the carbon black and a rubber molecular chain is formed.
6. The composite masterbatch prepared by the invention solves the problems of dispersion of the nano material, strengthening the interface action between the nano material and the matrix to a certain extent, and overcomes the defects of low elongation, high viscosity, poor processability and the like of the polymer nano composite material. The conductive rubber composition has the characteristics of high conductivity, high wear resistance, high dispersion and the like when being applied to rubber materials, and meets the requirement of higher mechanical property of rubber composite materials.
Drawings
FIG. 1 is an electron microscope scanning image of a composite masterbatch prepared in example 1 of the present invention;
FIG. 2 is an infrared spectrum of a composite masterbatch prepared in example 1 of the present invention;
FIG. 3 is a comparison of the performance of the composite masterbatch prepared in example 1 of the present invention in an all steel tread band.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
It should be noted that: in the present application, all embodiments and preferred methods mentioned herein can be combined with each other to form new solutions, if not specifically stated. In the present application, all the technical features mentioned herein and preferred features may be combined with each other to form new solutions, if not specifically stated. In the present application, percentages (%) or parts refer to percent by weight or parts by weight relative to the composition, unless otherwise specified. In the present application, the components referred to or the preferred components thereof may be combined with each other to form new embodiments, if not specifically stated. In this application, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "6-22" indicates that all real numbers between "6-22" have been listed herein, and "6-22" is only a shorthand representation of the combination of these numbers. The "ranges" disclosed herein may be in the form of lower limits and upper limits, and may be one or more lower limits and one or more upper limits, respectively. In the present application, the individual reactions or process steps may be performed sequentially or in sequence, unless otherwise indicated. Preferably, the reaction processes herein are carried out sequentially.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present application.
The test materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
In the quantitative tests in the following examples, three replicates were set, and the data are the mean or the mean ± standard deviation of the three replicates.
Example 1
Preparing a carbon nano tube suspension: mixing 5g of carbon tubes and 1000ml of water, putting the mixture into an oxidation reaction kettle, shearing the mixture at a high speed by using a thickened band saw blade for 20min to obtain a short carbon tube suspension with the length of 100 nm-10 mu m, then starting an oxidation circulation system and a water cooling system, keeping the concentration of ozone at 5g/L, keeping the temperature of liquid at 5-25 ℃, and performing cyclic oxidation for 20min to obtain a carbon tube suspension with a certain oxidation degree; wherein the ozone can also be one of oxygen, fluorine, chlorine and nitrogen dioxide;
adding 40g of carbon black into the suspension, stirring by adopting a parallel stirring blade, adjusting the stirring speed, stirring for 30-250 min to fully mix the carbon black with the oxidizing liquid, stirring with 1g of silane coupling agent in a reaction kettle, and carrying out coupling grafting modification to obtain surface-modified composite slurry; wherein the silane coupling agent can be one of a sulfur-containing silane coupling agent, an amino silane coupling agent, a vinyl silane coupling agent, an epoxy silane coupling agent, (meth) acryloyloxy silane coupling agent, an isocyanate-containing silane coupling agent, a long-chain alkyl silane coupling agent and an unsaturated coupling agent;
100g of natural rubber latex is added into the composite slurry for 400 r.min -1 Uniformly dispersing at the stirring speed, transferring into a water bath at 60 ℃ for volatilization and solidification, and drying the solidified rubber sheet in a vacuum drying oven at 60 ℃ for 9 hours to obtain the composite masterbatch.
Example 2
Preparing a carbon nano tube suspension: mixing 10g of carbon tubes with 1500ml of water, putting the mixture into an oxidation reaction kettle, shearing the mixture at a high speed by using a thickened band saw blade for 30min to obtain a short carbon tube suspension with the length of 50 nm-10 mu m, then starting an oxidation circulation system and a water cooling system, keeping the concentration of ozone at 6g/L, keeping the temperature of the liquid at 10-35 ℃, and circularly oxidizing for 30min to obtain a carbon tube suspension with a certain oxidation degree; wherein the oxidizing gas is one of oxygen, ozone, fluorine, chlorine and nitrogen dioxide;
adding 50g of carbon black into the suspension, stirring by adopting a parallel stirring blade, adjusting the stirring speed, stirring for 30-250 min to fully mix the carbon black with the oxidizing liquid, stirring with 3g of amino boric acid ester in a reaction kettle, and carrying out coupling grafting modification to obtain surface-modified composite slurry;
after the composite slurry is removed from the liquid outlet, the composite slurry is sprayed into 120g of pre-vulcanized natural rubber latex by a high-pressure pump for 400 r.min -1 Uniformly dispersing at the stirring speed, transferring into 40 deg.C water bath for volatilization and solidification, and drying the solidified film in 60 deg.C vacuum drying oven for 12 hrAnd obtaining the composite masterbatch.
Example 3
Preparing a carbon nano tube suspension: mixing 5g of carbon tubes and 100ml of water, putting the mixture into an oxidation reaction kettle, shearing the mixture at a high speed by using a thickened band saw blade for 30min to obtain a short carbon tube suspension liquid with the length of 10-50 mu m, then starting an oxidation circulation system and a water cooling system, keeping the concentration of ozone at 6g/L, keeping the temperature of the liquid at 25-40 ℃, and performing cyclic oxidation for 30min to obtain a carbon tube suspension liquid with a certain oxidation degree; wherein the oxidizing gas is one of oxygen, ozone, fluorine, chlorine and nitrogen dioxide;
adding 50g of silicon dioxide into the suspension, stirring by adopting a parallel stirring blade for 30-250 min, adjusting the stirring speed to fully mix the carbon black with the oxidizing liquid, stirring with 3g of silicon-boron coupling agent in a reaction kettle, and carrying out coupling grafting modification to obtain the surface-modified composite slurry.
After the composite slurry is removed from a liquid outlet, the composite slurry is sprayed into 120g of pre-vulcanized concentrated natural rubber latex by a high-pressure pump for 400 r.min -1 Uniformly dispersing at the stirring speed, transferring into a water bath at 70 ℃ for volatilization and solidification, and drying the solidified rubber sheet in a vacuum drying oven at 60 ℃ for 6 hours to obtain the composite masterbatch.
Example 4
Preparing a carbon nano tube suspension: mixing 10g of carbon tubes and 1500ml of water, putting the mixture into an oxidation reaction kettle, shearing the mixture at a high speed by using a thickened band saw blade for 30min to obtain a short carbon tube suspension liquid with the length of 50 nm-10 mu m, then starting an oxidation circulation system and a water cooling system, oxidizing the suspension liquid with the concentration of 6g/L, keeping the liquid temperature at 10-35 ℃, and performing cyclic oxidation for 30min to obtain a carbon tube suspension liquid with a certain oxidation degree; wherein the oxidizing gas is one of oxygen, ozone, fluorine, chlorine and nitrogen dioxide;
adding 50g of silicon dioxide into the suspension, stirring by adopting a parallel stirring blade, adjusting the stirring speed, stirring for 30-250 min to fully mix the silicon dioxide with the oxidizing liquid, stirring with 3g of amino boric acid ester in a reaction kettle, and carrying out coupling grafting modification to obtain surface-modified composite slurry;
after the composite slurry is removed from the liquid outlet, the composite slurry is sprayed into 120g of pre-vulcanized natural rubber latex by a high-pressure pump for 400 r.min -1 Uniformly dispersing at the stirring speed, transferring into a water bath at 40 ℃ for volatilization and solidification, and drying the solidified rubber sheet in a vacuum drying oven at 60 ℃ for 12 hours to obtain the composite masterbatch.
Comparative example 1
Preparing a carbon nano tube suspension: mixing 5g of carbon tubes with 1000ml of water, putting the mixture into an oxidation reaction kettle, and shearing the mixture at a high speed by using a thickened serrated blade for 20min to obtain a short carbon tube suspension with the length of 100 nm-10 mu m;
adding 40g of carbon black into the suspension, stirring by adopting a parallel stirring blade, adjusting the stirring speed, stirring for 30-250 min to fully mix the carbon black with the oxidizing liquid, stirring with 1g of silane coupling agent in a reaction kettle, and carrying out coupling grafting modification to obtain the surface-modified composite slurry.
100g of natural rubber latex is added into the composite slurry for 400 r.min -1 Uniformly dispersing at the stirring speed, transferring into a water bath at 60 ℃ for volatilization and solidification, and drying the solidified rubber sheet in a vacuum drying oven at 60 ℃ for 9 hours to obtain the composite masterbatch.
Comparative example 2
Modification of carbon nanotubes: placing the carbon nano tube in a container, and introducing oxidizing gas for treatment for 3 days to obtain a modified carbon nano tube;
adding carbon black and water into the modified carbon nano tube, stirring by adopting a parallel stirring blade, adjusting the stirring speed, stirring for 30-250 min to fully mix the carbon black with the oxidizing liquid, stirring with 1g of silane coupling agent in a reaction kettle, and carrying out coupling grafting modification to obtain surface modified composite slurry;
adding 100g of natural rubber latex into the composite slurry, uniformly dispersing at the stirring speed of 400 r.min < -1 >, transferring into a water bath at 60 ℃ for volatilization and solidification, and drying the solidified rubber sheet in a vacuum drying oven at 60 ℃ for 9h to obtain the composite masterbatch.
Adding 40g of carbon black into the suspension, stirring by adopting a parallel stirring blade, adjusting the stirring speed, stirring for 30-250 min to fully mix the carbon black with the oxidizing liquid, stirring with 1g of silane coupling agent in a reaction kettle, and carrying out coupling grafting modification to obtain surface-modified composite slurry; wherein the silane coupling agent can be one of a sulfur-containing silane coupling agent, a vinyl silane coupling agent, an epoxy silane coupling agent, (meth) acryloyloxy silane coupling agent, an isocyanate-containing silane coupling agent, a long-chain alkyl silane coupling agent and an unsaturated coupling agent;
adding 100g of natural rubber latex into the composite slurry, uniformly dispersing at the stirring speed of 400 r.min < -1 >, transferring into a water bath at 60 ℃ for volatilization and solidification, and drying the solidified rubber sheet in a vacuum drying oven at 60 ℃ for 9h to obtain the composite masterbatch.
Comparative example 3
Preparing a carbon nano tube suspension: 5g of carbon tubes are added into 1000ml of water to be dispersed to prepare carbon tube suspension;
adding 40g of carbon black into the suspension, stirring by adopting a parallel stirring blade, adjusting the stirring speed, stirring for 30-250 min to fully mix the carbon black with the suspension, stirring with 1g of silane coupling agent in a reaction kettle, and carrying out coupling grafting modification to obtain the surface-modified composite slurry.
100g of natural rubber latex is added into the composite slurry for 400 r.min -1 Uniformly dispersing at the stirring speed, transferring into a water bath at 60 ℃ for volatilization and solidification, and drying the solidified rubber sheet in a vacuum drying oven at 60 ℃ for 9 hours to obtain the composite masterbatch.
As shown in fig. 1, it is an electron microscope scanning image of the composite master batch prepared in example 1. As can be seen from the scanning image of the electron microscope, a single carbon nano tube is uniformly inserted into the rubber macromolecule and the carbon black to form a mixture which takes the carbon nano tube as a bridge to connect the carbon black and the rubber molecular chain.
As shown in fig. 2, the infrared spectra of the composite masterbatch prepared in example 1 and comparative example 1 are shown. From the infrared spectrum, the oxygen is shownThe position of the stretching vibration peak of the C = C skeleton of the carbon nanotube after formation is shifted, and the original carbon black is 1593 cm -1 Oxidized and transferred to 1617 cm -1 The reason that the peak positions of the two are shifted is that the content of the adjacent hydroxyl on the polycyclic aromatic hydrocarbon is increased, infrared absorption is effectively induced through carbocyclic ring vibration, the increase of the content of the hydroxyl of the oxidized carbon nanotube is indirectly proved, and a stretching vibration peak of-C = O appears at the position 1718 cm-1, which indicates that the carbonyl peak appears on the oxidized carbon nanotube.
The performance of the finished rubber is shown in fig. 3, and the test result shows that compared with the original formula of the tread rubber, the composite master batch compounded by the method has no phenomena of viscosity increase and processing difficulty in the formula, the dispersion performance of the filler in the rubber is improved, and the tensile property, the tearing performance, the abrasion performance and the heat conduction and electric conduction performance of the vulcanized rubber are obviously improved. Compared with the application data in the comparative examples 1 to 3, the application data in the example 1 has obvious advantages in the tearing performance, the abrasion performance and the electric and heat conducting performance of vulcanized rubber, and fully shows that the method improves the dispersion of the carbon nano tube and the carbon black in the masterbatch.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and substitutions can be made without departing from the technical principle of the present invention, and these modifications and substitutions should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of high-dispersion carbon nano composite masterbatch is characterized by comprising the following steps:
s1, shearing the carbon nano tubes in the dispersion liquid to prepare a chopped carbon nano tube suspension;
s2, introducing an oxidizing gas to oxidize the short carbon tube suspension to obtain a short carbon nanotube oxidizing solution;
s3, adding the reinforcing material into the short-cut carbon nanotube oxidizing solution to prepare carbon nanotube slurry;
s4, adding a coupling agent into the carbon nano tube slurry to prepare composite slurry;
s5, dispersing the natural rubber latex into the composite slurry to prepare the carbon nano tube-natural rubber composite material;
s6, solidifying and drying the carbon nano tube-natural rubber composite material to obtain the high-dispersion carbon nano composite master batch.
2. The method for preparing the high-dispersion carbon nano composite masterbatch according to claim 1, wherein the dispersion liquid adopts water; the mass ratio of the carbon nano tube to the water is 1: 20-1: 200.
3. The preparation method of the high-dispersion carbon nano composite masterbatch according to claim 1, wherein the length of the carbon nano tube in the short carbon nano tube oxidation solution is 50 nm-50 μm.
4. The method of claim 1, wherein in step S2, the oxidizing gas is one of oxygen, ozone, fluorine, chlorine, and nitrogen dioxide; the oxidation reaction temperature is 5-40 ℃, and the oxidation time is 20-120 min.
5. The method as claimed in claim 1, wherein the reinforcing material in step S3 is carbon black or silica;
wherein the carbon black is carbon black for rubber; the nitrogen adsorption specific surface area of the silicon dioxide is 100m 2 /g~200m 2 /g。
6. The preparation method of the high-dispersion carbon nano composite masterbatch according to claim 1, wherein the reinforcing material is added with the chopped carbon nano tube oxidation solution in step S3, and then stirred and mixed for 30-250 min.
7. The method for preparing high-dispersion carbon nano composite masterbatch according to claim 1, wherein the coupling agent in step S4 is one of a silane coupling agent, an amino borate ester, and a silicon boron coupling agent.
8. The method of claim 1, wherein the natural rubber latex is pre-vulcanized in step S5.
9. The method for preparing a highly dispersed carbon nanocomposite masterbatch according to claim 1, wherein the dispersing in step S5 is specifically to spray the composite slurry with a high pressure pump to mix with the natural rubber latex, and uniformly disperse the mixture by stirring; the stirring speed is 400 r.min -1 。
10. The preparation method of the high-dispersion carbon nano composite masterbatch according to claim 1, wherein the solidification in the step S6 is water bath solidification at a temperature of 40-70 ℃; the drying is specifically vacuum drying for 6-12 h at 60 ℃.
CN202210496169.5A 2022-05-09 2022-05-09 Preparation method of high-dispersion carbon nano composite masterbatch Pending CN115028906A (en)

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US20180298221A1 (en) * 2010-12-14 2018-10-18 Molecular Rebar Design, Llc Epoxy resin dispersions comprising discrete carbon nanotubes
CN105860133A (en) * 2016-06-23 2016-08-17 上海绿韧新材料有限公司 Carbon tube masterbatch and application thereof to tire treads
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