CN110564016B - High-reinforcement rubber latex wet mixing composite material and preparation process thereof - Google Patents
High-reinforcement rubber latex wet mixing composite material and preparation process thereof Download PDFInfo
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Abstract
The invention relates to the technical field of rubber synthesis, in particular to a high-reinforcement rubber latex wet mixing composite material and a preparation process thereof, wherein the raw materials of the material comprise an amino acid aqueous solution, a carbon nano tube, carbon black, graphene and rubber latex, and the amino acid can generate pi-pi action with the carbon nano tube; the process comprises the following steps: preparing an amino acid aqueous solution; adding the carbon nano tube into the prepared amino acid aqueous solution; adding the carbon nano tube amino acid dispersion liquid into rubber latex, and uniformly demulsifying and mixing; the demulsifying material is dewatered and dried after being discharged by a creper; and banburying and rubber discharge. The invention adopts amino acid which can generate pi-pi action with the carbon nano tube to carry out surface modification on the carbon nano tube, and then carries out wet mixing with rubber latex, thereby obtaining uniformly dispersed mixed rubber and finally achieving excellent high reinforcement performance.
Description
Technical Field
The invention relates to the technical field of rubber synthesis, in particular to a high-reinforcement rubber latex wet mixing composite material and a preparation process thereof.
Background
Carbon nanotubes, which are one-dimensional nanomaterials having excellent physical and mechanical properties, are mainly coaxial circular tubes having several to several tens of layers of carbon atoms arranged in a hexagonal pattern. Carbon nanotubes have a very large aspect ratio, typically between 1-100nm in diameter and several microns to hundreds of microns in length. Due to the large length-diameter ratio, the carbon nano tube has excellent mechanical, electrical, electric conduction and heat conduction properties, so the carbon nano tube has wide potential application prospect in a plurality of fields such as catalyst carriers, rubber plastic composite materials, electrochemical materials, photoelectric sensing and the like.
The carbon nanotubes can be roughly classified into clustered carbon nanotubes, vertical array carbon nanotubes, and horizontal array carbon nanotubes. The agglomeration carbon nano tube is difficult to be effectively dispersed by means because of disordered self winding, thereby greatly reducing the contact area between the agglomeration carbon nano tube and a substrate and having not ideal application effect. The carbon nanotubes in the vertical or horizontal arrays have better orientation, but the sp surface of the carbon nanotubes is considered2The hybrid inertia still has the problem that the array carbon nano tubes are difficult to form effective combination with rubber molecules when being applied to rubber tires, so that the heat generation of the filler in the deformation of running is increased, and the rolling resistance cannot be controlled ideally. Researches show that the interface effect of the carbon nano tube and an application matrix can be improved and enhanced by realizing the surface functionalization of the carbon nano tube by means of strong acid oxidation, D-A grafting modification and the like, but the method has higher practical application cost and large environmental protection pressure, and most importantly, the enhancement effect has great difference from the expectation.
Based on the above, the novel rubber latex wet mixing composite material with the uniformly dispersed carbon nano tubes and the preparation process thereof have significance.
Disclosure of Invention
Aiming at the prior carbon nano tube because of self agglomeration or surface sp2The invention provides a rubber latex wet mixing composite material and a preparation process thereof, and solves the technical problems of difficult dispersion caused by hybrid inertia and high pollution of the existing carbon nanotube modification technology.
In a first aspect, the invention provides a wet-process mixing composite material adopting high-reinforcement rubber latex, the raw materials of the mixing composite material comprise an amino acid aqueous solution, carbon nano tubes, carbon black, graphene and rubber latex, the amino acid is an amino acid capable of generating pi-pi action with the carbon nano tubes, and the amino acid: carbon nanotube: carbon black: the mass ratio of the graphene is (0.1-10): (1-30): (0-50): (0-20).
Further, the amino acid is at least one of histidine, tryptophan, phenylalanine, tyrosine and valine;
the carbon nano tube is at least one of a single-walled carbon nano tube and a multi-walled carbon nano tube, and is preferably a directional array multi-walled carbon nano tube;
the specific surface area of the graphene is 500m2At least one of graphene oxide, thin-layer graphene and single-layer graphene with a specific surface area of 800-2Between/g of at least one of graphene oxide, thin-layer graphene, single-layer graphene;
the rubber latex is at least one of natural latex, polybutadiene latex and styrene-butadiene latex.
Further, the mass fraction of the amino acid in the amino acid aqueous solution is 0.2-5%, preferably 0.2-1%.
Further, the mixing composite material is rubber master batch or formula rubber added with auxiliary materials. The rubber master batch is a mixed composite material prepared by the steps of the processes S1-S4, and the formula rubber is a mixed composite material prepared by the steps S1-S7 and added with auxiliary materials.
In a second aspect, the invention provides a preparation process of a high-reinforcement rubber latex wet mixing composite material, which comprises the following steps:
s1: preparing an amino acid aqueous solution, wherein the amino acid can generate pi-pi action with the carbon nano tube;
s2: adding the carbon nano tube into the prepared amino acid aqueous solution, stirring and uniformly dispersing, wherein the amino acid: carbon nanotube: carbon black: the mass ratio of the graphene is (0.1-10): (1-30): (0-50): (0-20);
s3: adding the prepared carbon nano tube amino acid dispersion liquid into rubber latex at a high speed, and performing uniform demulsification and mixing to obtain a demulsification material;
s4: and (3) discharging the demulsifying material by a creper, squeezing water, and drying at 70-80 ℃.
Further, the amino acid is at least one of histidine, tryptophan, phenylalanine, tyrosine and valine;
the carbon nano tube is at least one of a single-walled carbon nano tube and a multi-walled carbon nano tube, and is preferably a directional array multi-walled carbon nano tube;
the specific surface area of the graphene is 500m2At least one of graphene oxide, thin-layer graphene and single-layer graphene with a specific surface area of 800-2Between/g of at least one of graphene oxide, thin-layer graphene, single-layer graphene;
the rubber latex is at least one of natural latex, polybutadiene latex and styrene-butadiene latex.
Further, the mass fraction of the amino acid in the amino acid aqueous solution is 0.2-5%, preferably 0.2-1%.
Further, the high-speed mixing in the S3 is high-speed mechanical mixing, and the speed is 500-5000 rpm; or two streams of liquid are mixed in high speed collision, the speed is 20-150m/s, preferably 50-120 m/s.
Further, the process also comprises the following steps:
s5: mixing the dried material with rubber auxiliary materials through an internal mixer, and discharging rubber;
s6: the materials after rubber removal are subjected to sheet loading and unloading in an open mill and are kept stand;
s7: and (3) continuously adding sulfur into the rubber sheet on an open mill for mixing, and finally discharging the rubber sheet.
Further, the rubber auxiliary material is at least one of a rubber anti-aging agent, a vulcanization accelerator, a peptizer and an activator.
The beneficial effect of the invention is that,
the invention provides a high-reinforcement rubber latex wet-process mixing composite material, vulcanized rubber is obtained by vulcanizing the material, compared with vulcanized rubber without amino acid treatment, the high-reinforcement rubber latex composite material has the advantages that the tensile strength, the tearing strength and the wear resistance are improved, the compression heat generation is obviously reduced, and the good high-reinforcement performance of the product is well embodied.
The invention also provides a preparation process of the high-reinforcement rubber latex wet-process mixing composite material, which comprises the steps of firstly carrying out pre-dispersion treatment on the amino acid aqueous solution with specific concentration and the carbon nano tubes, then mixing the carbon nano tube amino acid dispersion liquid with the rubber latex liquid phase at high speed, uniformly demulsifying, and carrying out links such as creping, drying and the like to finally obtain the mixing composite material with high reinforcement performance. The preparation process is simple and stable, the conditions are easy to control, the product uniformity is good, the batch stability is good, and the batch production can be realized; the beneficial effect of the method is that the method has the advantages that,
(1) the surface of the carbon nano tube is modified by pi-pi action of bioactive amino acid, so that the dispersibility of the carbon nano tube is effectively improved, and the proportion of bonding glue is greatly improved; meanwhile, the surface active sites of the carbon nanotubes are increased on the side by adsorbing and binding amino acid on the surfaces of the carbon nanotubes when the carbon nanotubes act with rubber, so that mechanical reinforcement is better performed.
The principle is as follows: under the pi-pi correlation effect formed by the amino acid and the surface of the carbon nano tube, the amino acid can be adsorbed and bound on the surface of the carbon nano tube, so that the van der Waals force effect between the carbon nano tubes is effectively blocked, and the dispersibility of the carbon nano tubes is well improved. Among them, histidine, tryptophan, phenylalanine, leucine, and valine have strong binding energy with carbon nanotubes, and can achieve good dispersion effect. The active sites on the surface of the carbon nano tube are aromatic ring structures at the edge of the carbon nano tube, and the amino acid improves the dispersibility of the carbon nano tube and increases the binding action points of the carbon nano tube and rubber, thereby being more beneficial to the high reinforcement performance of the carbon nano tube.
(2) And a wet mixing mode is adopted, so that the contact between materials is more sufficient, the dispersion of the compound is more uniform, the product is not easy to fly, and the environment is protected.
Drawings
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is an SEM image of a mixed composite material obtained by the preparation process of the present invention, wherein the magnification is 1 ten thousand times;
FIG. 2 is an SEM image of a compounded composite material obtained by the preparation process of the present invention, wherein the magnification is 3 ten thousand times.
Detailed Description
In order to make those skilled in the art better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A wet-process rubber latex mixing composite material is prepared from amino acid aqueous solution, carbon nanotubes, carbon black, graphene and rubber latex,
the mass fraction of amino acid in the amino acid aqueous solution is 0.25%, the types of the amino acid are phenylalanine and tyrosine, and the mass ratio of the phenylalanine to the tyrosine is 2: 1,
the carbon nano tube is an iron-based multi-wall carbon nano tube, the tube diameter is 10-30nm, and the specific surface area is 200-2/g，
The specific surface area of the graphene is 500-700m2Per g of graphene oxide prepared by a physical method,
amino acids: carbon nanotube: carbon black: the mass ratio of the graphene is 2.5: 6: 40: 3,
the rubber latex is natural latex with solute mass fraction of 3 percent,
the auxiliary materials comprise 129g of zinc oxide, 64g of stearic acid and 64g of sulfur.
The preparation process of the mixing composite material comprises the following steps:
s1: preparing 40L of amino acid aqueous solution with the mass fraction of 0.25% of amino acid in a 100L clean container;
s2: according to the amino acid: carbon nanotube: carbon black: the mass of the graphene is 2.5: 6: 40: 3, weighing corresponding materials according to the proportion, adding the carbon nano tube, the carbon black and the graphene into the prepared amino acid aqueous solution, and stirring for 30 min;
s3: 107kg of natural latex with solute mass fraction of 3 percent is added into a 200L reaction kettle, and stirring is started to adjust to 5000 rpm; quickly pouring the prepared carbon nano tube amino acid dispersion liquid into a reaction kettle, keeping 5000rpm and stirring for 8min, reducing the rotating speed to 1000rpm, keeping the rotating speed for 10min, and uniformly demulsifying and mixing;
s4: the demulsifying material is squeezed by a roller of a creper and then dried for 15h at 75 ℃;
s5: mixing the dried material with 129g of zinc oxide and 64g of stearic acid by an internal mixer, and carrying out internal mixing until the temperature is 120 ℃ for rubber discharge;
s6: the materials after the rubber removal are fed into an open mill and placed on a wood board for standing for 4-6 hours;
s7: and (3) continuously adding 64g of sulfur into the rubber sheet on an open mill for mixing, and finally discharging the rubber sheet to obtain the high-reinforcement rubber latex wet mixing composite material.
And vulcanizing the mixed composite material at the temperature of 150 ℃ to finally obtain 2.6kg of vulcanized rubber.
Example 2
A rubber latex wet mixing composite material comprises amino acid aqueous solution, carbon nano tubes, carbon black and rubber latex, wherein the mass fraction of amino acid in the amino acid aqueous solution is 0.6 percent,
amino acids: carbon nanotube: the mass ratio of the carbon black is 3: 10: 35, the amino acid types are phenylalanine, valine and tryptophan, and the mass ratio of the phenylalanine, the valine and the tryptophan is 1: 1: 1,
the carbon nano tube is an iron-based multi-wall carbon nano tube with the tube diameter of 2-5nm and the specific surface area of 1100-1550m2/g，
The rubber latex is natural latex with 5 percent of solute mass fraction,
the auxiliary materials comprise 400g of zinc oxide, 200g of stearic acid and 200g of sulfur.
The preparation process of the mixing composite material comprises the following steps:
s1: 50L of amino acid aqueous solution with the mass fraction of 0.6 percent of amino acid is prepared in a 100L clean container;
s2: according to the amino acid: carbon nanotube: the mass of the carbon black is 3: 10: 35, weighing corresponding materials according to the proportion, adding the carbon nano tube and the carbon black into the prepared amino acid aqueous solution, and stirring for 50 min;
s3: 200kg of natural latex with solute mass fraction of 5 percent is added into a 300L reaction kettle, and stirring is started to adjust to 4000 rpm; quickly pouring the prepared carbon nano tube amino acid dispersion liquid into a reaction kettle, keeping 4000rpm for stirring for 10min, reducing the rotating speed to 800rpm, keeping for 15min, and uniformly demulsifying and mixing;
s4: the demulsifying material is rolled and squeezed by a creper and then dried for 20 hours at 70 ℃;
s5: mixing the dried material with 400g of zinc oxide and 200g of stearic acid by an internal mixer, and carrying out internal mixing until the temperature is 120 ℃ for rubber discharge;
s6: the materials after the rubber removal are fed into an open mill and placed on a wood board for standing for 4-6 hours;
s7: and (3) continuously adding 200g of sulfur into the rubber sheet on an open mill for mixing, and finally discharging the rubber sheet to obtain the high-reinforcement rubber latex wet mixing composite material.
And vulcanizing the mixed composite material at the temperature of 150 ℃ to finally obtain 15.3kg of vulcanized rubber.
Example 3
A wet-process mixing composite material of rubber latex is prepared from amino acid aqueous solution, carbon nanotubes and rubber latex,
the mass fraction of amino acid in the amino acid aqueous solution is 0.8%, the types of the amino acid are histidine and tryptophan, and the mass ratio of the histidine to the tryptophan is 2: 3,
the carbon nano tube is a cobalt multi-walled carbon nano tube with the tube diameter of 5-10nm and the specific surface area of 300-2/g，
Amino acids: the mass ratio of the carbon nano tube is 2: 10,
the rubber latex is natural latex with 5 percent of solute mass fraction.
The preparation process of the mixing composite material comprises the following steps:
s1: 50L of amino acid aqueous solution with the mass fraction of 0.8 percent of amino acid is prepared in a 100L clean container;
s2: according to the amino acid: the mass of the carbon nano tube is 2: 10, weighing corresponding materials, adding the carbon nano tube into the prepared amino acid aqueous solution, and stirring for 45 min;
s3: preparing 160kg of natural latex with solute mass percent of 5%, mixing the natural latex and the carbon nano tube amino acid aqueous solution in a high-speed collision mode at the speed of 100m/s, and uniformly demulsifying and mixing;
s4: and (3) squeezing the demulsifying material by a roller of a crepe machine, drying for 18h at 80 ℃, and weighing 9.8kg of rubber master batch after drying.
Comparative example 1
A rubber latex wet mixing composite material, which replaces the amino acid aqueous solution in the embodiment 1 with deionized water, comprises the raw materials of deionized water, carbon nano tubes, carbon black, graphene and rubber latex,
the carbon nano tube is an iron-based multi-wall carbon nano tube, the tube diameter is 10-30nm, and the specific surface area is 200-2/g，
The specific surface area of the graphene is 500-700m2Per g of graphene oxide prepared by a physical method,
carbon nanotube: carbon black: the mass ratio of the graphene is 6: 40: 3,
the rubber latex is natural latex with solute mass fraction of 3 percent,
the auxiliary materials comprise 129g of zinc oxide, 64g of stearic acid and 64g of sulfur.
The preparation process of the mixing composite material comprises the following steps:
s1: adding 40L of deionized water into a 100L clean container;
s2: weighing 240g of carbon nanotubes, and according to the weight ratio of the carbon nanotubes: carbon black: the mass of the graphene is 6: 40: 3, weighing corresponding materials according to the proportion, adding the carbon nano tube, the carbon black and the graphene into deionized water, and stirring for 30 min;
s3: 107kg of natural latex with solute mass fraction of 3 percent is added into a 200L reaction kettle, and stirring is started to adjust to 5000 rpm; quickly pouring the prepared carbon nano tube dispersion liquid into a reaction kettle, keeping 5000rpm for stirring for 8min, reducing the rotating speed to 1000rpm, keeping the rotating speed for 10min, and uniformly demulsifying and mixing;
s4: the demulsifying material is squeezed by a roller of a creper and then dried for 15h at 75 ℃;
s5: mixing the dried material with 129g of zinc oxide and 64g of stearic acid by an internal mixer, and carrying out internal mixing until the temperature is 120 ℃ for rubber discharge;
s6: the material after the rubber removal is fed into an open mill and placed on a wood board for standing for 4-6 hours after being fed;
s7: and (3) continuously adding 64g of sulfur into the rubber sheet on an open mill for mixing, and finally discharging to obtain the high-reinforcement rubber latex wet mixing composite material.
And vulcanizing the mixed composite material at the temperature of 150 ℃ to finally obtain 2.5kg of vulcanized rubber.
Test example 1
The vulcanized rubbers finally obtained in example 1 and comparative example 1 were subjected to vulcanization time and physical property tests, and the test results are shown in table 1 below.
TABLE 1 vulcanized rubber vulcanization time and physical Property test results
As can be seen from the table, under the same formula conditions, the vulcanization process of the rubber compound of the example 1 is obviously shortened, the vulcanization efficiency is improved, and the resources and the energy consumption are saved; compared with vulcanized rubber without the treatment, the vulcanized rubber treated by the amino acid has obviously improved physical properties such as tensile strength, tearing strength, wear resistance and the like; the tan delta of the vulcanized rubber of the example 1 is greatly reduced at the temperature of 60 ℃, which shows that the interfacial force between the carbon nanotube and the rubber is strong, and the heat generation is obviously reduced.
Although the present invention has been described in detail in connection with the preferred embodiments with reference to the accompanying drawings, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions should be within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present disclosure and the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. A preparation process of a high-reinforcement rubber latex wet mixing composite material is characterized by comprising the following steps:
s1: preparing an amino acid aqueous solution, wherein the amino acid is at least one of histidine, tryptophan, leucine and valine;
s2: adding the multi-wall carbon nano tube and carbon black into the prepared amino acid aqueous solution, stirring and uniformly dispersing, wherein the amino acid: multi-walled carbon nanotubes: the mass ratio of the carbon black is (0.1-10): (1-30): (0-50);
s3: adding the prepared multi-walled carbon nanotube amino acid dispersion liquid into rubber latex at a high speed, and performing uniform demulsification and mixing to obtain a demulsification material;
s4: and (3) discharging the demulsifying material by a creper, squeezing water, and drying at 70-80 ℃.
2. The process for preparing a highly reinforced rubber latex wet-mixing composite material as claimed in claim 1, wherein;
the rubber latex is at least one of natural latex, polybutadiene latex and styrene-butadiene latex.
3. The process of claim 2, wherein the multi-walled carbon nanotubes are oriented multi-walled carbon nanotubes.
4. The process for preparing a highly reinforced rubber latex wet mixing composite material as claimed in claim 1, wherein the mass fraction of amino acids in the amino acid aqueous solution is 0.2% -5%.
5. The process for preparing a highly reinforced rubber latex wet mixing composite material as claimed in claim 4, wherein the mass fraction of amino acid in the amino acid aqueous solution is 0.2% -1%.
6. The process for preparing a highly reinforced rubber latex wet mixing composite material as claimed in claim 1, wherein the high speed mixing in S3 is high speed mechanical mixing, the speed is 500-5000 rpm;
or two liquid streams are mixed in a high-speed collision way, and the speed is 20-150 m/s.
7. The process for preparing a highly reinforced rubber latex wet-mixing composite material as claimed in claim 1, wherein said high-speed mixing in S3 is a high-speed collision mixing of two liquids at a speed of 50-120 m/S.
8. The process for preparing a highly reinforced rubber latex wet-mixing composite material according to claim 1, wherein the process further comprises the steps of:
s5: mixing the dried material with rubber auxiliary materials through an internal mixer, and discharging rubber;
s6: the materials after rubber removal are subjected to sheet loading and unloading in an open mill and are kept stand;
s7: and (3) continuously adding sulfur into the rubber sheet on an open mill for mixing, and finally discharging the rubber sheet.
9. The process of claim 8, wherein the rubber auxiliary material is at least one of rubber antioxidant, vulcanization accelerator, peptizer and activator.
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