CN115418097A - High-strength modified nano composite rubber material and preparation method thereof - Google Patents
High-strength modified nano composite rubber material and preparation method thereof Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/041—Carbon nanotubes
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- 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
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention relates to a high-strength modified nano composite rubber material and a preparation method thereof, belonging to the technical field of high polymer materials. The material comprises the following raw materials: 100 parts of polyurethane rubber, 50-60 parts of modified carbon nano tube, 1-5 parts of zinc oxide, 0.5-3 parts of stearic acid, 0.5-1 part of accelerator and 0.5-1 part of additive. According to the preparation method, the hydroxylated multi-wall carbon nano tube is modified by dicyclohexylmethane diisocyanate and then is blended with the polyurethane rubber, the hydroxyl in the hydroxylated multi-wall carbon nano tube is reacted with the isocyanate group in the dicyclohexylmethane diisocyanate to be connected, and meanwhile, the dicyclohexylmethane diisocyanate connected with the hydroxylated multi-wall carbon nano tube acts with the polyurethane rubber through a hydrogen bond, so that the modified carbon nano tube is well dispersed in a polyurethane matrix, and the material shows high toughness and tensile strength.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a high-strength modified nano composite rubber material and a preparation method thereof.
Background
The raw polyurethane rubber is prepared from diisocyanate and polyether glycol according to the mass ratio of-NCO to-OH. The polyurethane rubber not only has high strength and low permanent deformation characteristics, but also has the advantages of simple process, high production efficiency and the like, and the structural characteristics of the polyurethane rubber molecule not only determine that the polyurethane rubber has valuable comprehensive physical and mechanical properties, but also can adjust the elasticity, cold resistance, modulus, hardness, mechanical strength and other properties by changing the components and relative molecular mass of the raw materials and the ester ratio of the raw materials. The rubber has high tensile strength (generally 28-42MPa, and the highest tensile strength can reach 70 MPa) and tear strength; the elasticity is excellent, and even when the hardness is high, the elasticity is high; the elongation at break is very large, generally can reach 400% -600%, and the maximum can reach 1000%; has a wide hardness range, the minimum is Shore (A) 10, and most of Shore (A) 45-95. When the hardness is Yu Shaoer (A) 70, the tensile strength and the stress at definite elongation are higher than those of natural rubber, and when the hardness reaches 80-90 Shore (A), the tensile strength, the tear strength and the stress at definite elongation are good. Polyurethane rubbers are widely used in the fields of the mechanical industry, the automobile industry, the petroleum industry, the mining industry, the electrical and instrument industry, the leather and shoe industry, the construction industry, and the manufacture of medical and sports goods.
The raw rubber has insufficient practical strength, only the reinforced rubber can be applied to various products, and the rubber material can obtain good strength and application flexibility by adding the filler for reinforcement. The carbon nano tube is a material which can be prepared at present and has the highest specific strength, and if other engineering materials are used as a matrix and are made into a composite material with the carbon nano tube, the composite material can show good strength, elasticity, fatigue resistance and isotropy, so that the performance of the composite material is greatly improved. The carbon nano tube has the characteristics of larger length-diameter ratio, larger specific surface area, large surface energy and the like, so that the carbon nano tube is easy to generate winding agglomeration, and the application of the carbon nano tube in rubber is hindered. In order to improve the dispersibility of carbon nanotubes in rubber and to exert greater advantages in polymer materials such as rubber, it is necessary to modify carbon nanotubes.
Disclosure of Invention
The invention relates to a high-strength modified nano composite rubber material and a preparation method thereof, belonging to the technical field of high polymer materials. The material comprises the following raw materials in parts by weight: 100 parts of polyurethane rubber, 50-60 parts of modified carbon nano tubes, 1-5 parts of zinc oxide, 0.5-3 parts of stearic acid, 0.5-1 part of accelerator and 0.5-1 part of additive. The application also discloses a preparation method of the high-strength modified nano composite rubber material. According to the preparation method, the hydroxylated multi-wall carbon nano tube is modified by dicyclohexylmethane diisocyanate and then is blended with the polyurethane rubber, the hydroxyl in the hydroxylated multi-wall carbon nano tube is reacted with the isocyanate group in the dicyclohexylmethane diisocyanate to be connected, and meanwhile, the dicyclohexylmethane diisocyanate connected with the hydroxylated multi-wall carbon nano tube acts with the polyurethane rubber through a hydrogen bond, so that the modified carbon nano tube is well dispersed in a polyurethane matrix, and the material shows high toughness and tensile strength. The purpose of the invention can be realized by the following technical scheme:
a high-strength modified nano composite rubber material comprises the following raw materials in parts by weight: 100 parts of polyurethane rubber, 50-60 parts of modified carbon nano tubes, 1-5 parts of zinc oxide, 0.5-3 parts of stearic acid, 0.5-1 part of accelerator and 0.5-1 part of additive.
The preparation method of the modified carbon nano tube comprises the following steps:
the method comprises the following steps of (1) charging dicyclohexylmethane diisocyanate and N, N-dimethylformamide into a container, magnetically stirring and heating to 50-60 ℃ (the using ratio of dicyclohexylmethane diisocyanate to hydroxylated multiwalled carbon nanotube suspension is 8g; slowly adding the hydroxylated multi-walled carbon nanotube suspension into a reaction vessel, dropwise adding dibutyltin dilaurate, and stirring and reacting at 50-60 ℃ for more than 8 hours; centrifuging the reacted mixture, washing the mixture by N, N-dimethylformamide for many times, and washing away unreacted dicyclohexyl methane diisocyanate; and (3) putting the reactant into a vacuum oven at 40-60 ℃ for drying for more than 4h to obtain the modified carbon nanotube.
More preferably, the dibutyltin dilaurate is added in an amount of 3 to 4 drops per 8g dicyclohexylmethane diisocyanate.
More preferably, the temperature of the vacuum oven is set to 50 ℃.
The preparation method of the hydroxylated multi-wall carbon nanotube suspension comprises the following steps:
putting a hydroxylated multi-walled carbon nanotube into a digestion tube, adding N, N-dimethylformamide, and dispersing under the action of ultrasound; the dosage ratio of the hydroxylated multi-walled carbon nanotube to the N, N-dimethylformamide is 100 mg: 25mLN, N-dimethylformamide.
More preferably, the accelerator is dimethyl-thio-toluenediamine.
More preferably, the additive is toluene diisocyante.
The preparation method of the high-strength modified nano composite rubber material comprises the following steps:
s1: placing the polyurethane rubber in an open mill, thinly passing the polyurethane rubber until the rubber has plasticity, and generating proper stacking rubber by adjusting a rubber baffle plate and a roller spacing; adding zinc oxide, and uniformly mixing the zinc oxide and the master batch by using rubber tapping, rubber turning and other modes;
s2: adding modified carbon nano tube, accelerant, additive and stearic acid, and uniformly mixing the mixture and master batch in the modes of rubber tapping, rubber turning and the like;
s3: adjusting the roller distance to be small, further uniformly mixing the materials in a triangular packaging or rolling mode, thinly passing the materials for 6 to 8 times, and then discharging the materials;
s4: vulcanizing the obtained rubber by a flat vulcanizing machine at the vulcanization temperature of 80-120 ℃, the vulcanization pressure of 20MPa and the vulcanization time of 45-75min, and putting the molded rubber into a 100 ℃ oven for vulcanization for more than 24h to prepare the high-strength modified nano composite rubber material.
The invention has the beneficial effects that:
the basic network of carbon nanotubes is composed of one of the strongest bonds in nature, and C = = C covalent bond formed by sp2 hybridization, as with graphene. The carbon nano tube has extremely high strength and extremely high toughness, the tensile strength of the carbon nano tube reaches 50-200GPa, which is 100 times of that of steel, the density of the carbon nano tube is only 1/6 of that of the steel, and the tensile strength of the carbon nano tube with a single-layer wall with an ideal structure is about 800GPa; its elastic modulus is up to 1TPa, which is about 5 times that of steel and about 20 times that of carbon fiber, and has very good flexibility. The average Young modulus of the carbon nano tube is 1.8TPa, and the bending strength is 14.2GPa. Since the carbon nanotube has a hollow cage-like structure, it can realize its elasticity by volume change, and thus can withstand a tensile strain of 40% without exhibiting brittle behavior, plastic deformation or bond rupture.
Dicyclohexylmethane diisocyanate is connected with the hydroxylated carbon nano-tube through reaction, and besides, the short chain of isocyanate and the adjacent polyurethane molecular chain can form hydrogen bond interaction. The modified carbon nano tube is well dispersed in the polyurethane matrix, the dispersibility of the carbon nano tube in a liquid medium and the compatibility of the carbon nano tube with a polymer matrix can be improved through modification, and the good stress transfer efficiency can be ensured under the action of external force.
Hydrogen bond action between molecular chains is used as a sacrificial bond to break first to dissipate a large amount of energy; the hydrogen bond and the coordination bond are easy to break and dissipate energy when being acted by a loading force due to low bond energy, and the breakage and reconstruction of the sacrificial bond provide continuous energy dissipation, thereby realizing the reinforcement and toughening of the elastomer; together with the hidden length, is also released, and the material therefore exhibits high toughness and tensile strength.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to 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 method for manufacturing the modified carbon nanotube comprises the following steps:
100mg of hydroxylated multi-wall carbon nano-tube is put into a digestion tube, 25mLN is added, and N-dimethylformamide is dispersed under the ultrasonic action to prepare a hydroxylated multi-wall carbon nano-tube suspension;
8g of dicyclohexylmethane diisocyanate and 15mLN, N-dimethylformamide were charged into a vessel, stirred magnetically and heated to 50 ℃; slowly adding the prepared hydroxylated multi-walled carbon nanotube suspension into a reaction vessel, dropwise adding 3 drops of dibutyltin dilaurate, and keeping the temperature at 50 ℃ for stirring and reacting for 8 hours; centrifuging the reacted mixture, washing the mixture for many times by using N, N-dimethylformamide, and washing away unreacted dicyclohexylmethane diisocyanate; and (3) putting the reactant into a vacuum oven at 40 ℃ for drying for 4h to obtain the modified carbon nanotube.
Example 2
A method for manufacturing the modified carbon nanotube comprises the following steps:
100g of hydroxylated multi-wall carbon nano-tube is put into a digestion tube, 25LN is added, and N-dimethylformamide is dispersed under the action of ultrasound to prepare a hydroxylated multi-wall carbon nano-tube suspension;
9g of dicyclohexylmethane diisocyanate and 15mLN, N-dimethylformamide were charged into a vessel, magnetically stirred and heated to 55 ℃; slowly adding the prepared hydroxylated multi-walled carbon nanotube suspension into a reaction vessel, dropwise adding 3.5 drops of dibutyltin dilaurate, and keeping the temperature at 55 ℃ for stirring reaction for 8 hours; centrifuging the reacted mixture, washing the mixture for many times by using N, N-dimethylformamide, and washing away unreacted dicyclohexylmethane diisocyanate; and (3) putting the reactant into a vacuum oven at 50 ℃ for drying for 5h to obtain the modified carbon nanotube.
Example 3
A method for manufacturing the modified carbon nanotube comprises the following steps:
100mg of hydroxylated multi-wall carbon nano-tube is put into a digestion tube, 25mLN is added, and N-dimethylformamide is dispersed under the ultrasonic action to prepare a hydroxylated multi-wall carbon nano-tube suspension;
10g of dicyclohexylmethane diisocyanate and 15mLN, N-dimethylformamide were charged into a vessel, magnetically stirred and heated to 60 ℃; slowly adding the prepared hydroxylated multi-walled carbon nanotube suspension into a reaction vessel, dropwise adding 4 drops of dibutyltin dilaurate, and keeping the temperature at 60 ℃ for stirring and reacting for 8 hours; centrifuging the reacted mixture, washing the mixture for many times by using N, N-dimethylformamide, and washing away unreacted dicyclohexylmethane diisocyanate; and (3) putting the reactant into a vacuum oven at 60 ℃ for drying for 6 hours to obtain the modified carbon nano tube.
Example 4
Preparation method of high-strength modified nano composite rubber material
S1: 200g of polyurethane rubber is placed in an open mill, the polyurethane rubber is thinned to ensure that the rubber has plasticity, and proper accumulation rubber is generated by adjusting a rubber baffle plate and a roller spacing; adding 2g of zinc oxide, and uniformly mixing the zinc oxide with the masterbatch in a rubber tapping and rubber turning mode;
s2: adding the modified carbon nano tube in the embodiment 1, adding 1g of promoter dimethylthiotoluenediamine, 1g of additive toluene diisocynate and 3g of stearic acid, and uniformly mixing the mixture and master batch in a rubber tapping and rubber turning mode;
s3: adjusting the roller distance to be small, further uniformly mixing the materials in a triangular bag making or rolling mode, and carrying out thin passing for 6 times and then carrying out sheet discharging;
s4: vulcanizing the obtained rubber by a flat vulcanizing machine, wherein the vulcanizing temperature is 80 ℃, the vulcanizing pressure is 20MPa, the vulcanizing time is 45min, and putting the molded rubber into a 100 ℃ oven for vulcanizing for 24h to prepare the high-strength modified nano composite rubber material.
Example 5
Preparation method of high-strength modified nano composite rubber material
S1: 200g of polyurethane rubber is placed in an open mill, the polyurethane rubber is thinned to ensure that the rubber has plasticity, and proper accumulation rubber is generated by adjusting a rubber baffle plate and a roller spacing; adding 6g of zinc oxide, and uniformly mixing the zinc oxide and the master batch by using a rubber tapping and rubber turning mode;
s2: adding the modified carbon nano tube in the embodiment 2, adding 1.5g of promoter dimethylthio toluene diamine, 1.5g of additive toluene diisocynate and 4.5g of stearic acid, and uniformly mixing the mixture and master batch in a rubber tapping and rubber turning mode;
s3: adjusting the roller distance to be small, further uniformly mixing the materials in a triangular bag making or rolling mode, and discharging the sheets after 6 times of thin passing;
s4: vulcanizing the obtained rubber by a flat vulcanizing machine at 100 ℃, the vulcanization pressure is 20MPa, the vulcanization time is 60min, and putting the molded rubber into a 100 ℃ oven for vulcanization for 24h to obtain the high-strength modified nano composite rubber material.
Example 6
Preparation method of high-strength modified nano composite rubber material
S1: 200g of polyurethane rubber is placed in an open mill, the polyurethane rubber is thinned to ensure that the rubber has plasticity, and proper accumulation rubber is generated by adjusting a rubber baffle plate and a roller spacing; adding 10g of zinc oxide, and uniformly mixing the zinc oxide and the master batch by using a rubber tapping and rubber turning mode;
s2: adding the modified carbon nano tube obtained in the example 3, adding 2g of promoter dimethylthiotoluenediamine, 2g of additive toluene diisocyanide and 6g of stearic acid, and uniformly mixing the mixture and master batch in a rubber tapping and rubber turning manner;
s3: adjusting the roller distance to be small, further uniformly mixing the materials in a triangular bag making or rolling mode, and carrying out thin passing for 6 times and then carrying out sheet discharging;
s4: vulcanizing the obtained rubber by a flat vulcanizing machine at the vulcanization temperature of 120 ℃, the vulcanization pressure of 20MPa and the vulcanization time of 75min, and putting the molded rubber into a 100 ℃ oven for vulcanization for 24h to prepare the high-strength modified nano composite rubber material.
Comparative example 1
Preparation method of high-strength rubber material
S1: 200g of polyurethane rubber is placed in an open mill, the polyurethane rubber is thinned to ensure that the rubber has plasticity, and proper accumulation rubber is generated by adjusting a rubber baffle plate and a roller spacing; adding 2g of zinc oxide, and uniformly mixing the zinc oxide with the masterbatch in a rubber tapping and rubber turning mode;
s2: adding 1g of promoter dimethylthiotoluenediamine, 1g of additive toluene diisocynate and 3g of stearic acid, and uniformly mixing the mixture and master batch in a rubber tapping and rubber turning manner;
s3: adjusting the roller distance to be small, further uniformly mixing the materials in a triangular bag making or rolling mode, and carrying out thin passing for 6 times and then carrying out sheet discharging;
s4: vulcanizing the obtained rubber by a flat vulcanizing machine at the vulcanization temperature of 80 ℃, the vulcanization pressure of 20MPa and the vulcanization time of 45min, and putting the molded rubber into a 100 ℃ oven for vulcanization for 24h to prepare the high-strength modified nano composite rubber material.
Comparative example 2
Preparation method of high-strength nano rubber material
S1: 200g of polyurethane rubber is placed in an open mill, the polyurethane rubber is thinned to ensure that the rubber has plasticity, and proper accumulation rubber is generated by adjusting a rubber baffle plate and a roller spacing; adding 2g of zinc oxide, and uniformly mixing the zinc oxide with the masterbatch in a rubber tapping and rubber turning mode;
s2: adding 100g of multi-wall carbon nano tube, adding 1g of promoter dimethylthiotoluenediamine, 1g of additive toluene diisocynate and 3g of stearic acid, and uniformly mixing the mixture and master batch in a rubber tapping and rubber turning mode;
s3: adjusting the roller distance to be small, further uniformly mixing the materials in a triangular bag making or rolling mode, and discharging the sheets after 6 times of thin passing;
s4: vulcanizing the obtained rubber by a flat vulcanizing machine at the vulcanization temperature of 80 ℃, the vulcanization pressure of 20MPa and the vulcanization time of 45min, and putting the molded rubber into a 100 ℃ oven for vulcanization for 24h to prepare the high-strength modified nano composite rubber material.
The following performance tests were performed for examples 4-6 and comparative example, respectively:
test example 1
And (3) testing fracture toughness property: a WD-10A electronic universal tester (Guangzhou tester factory) is used for testing the three-point bending fracture toughness test sample of the epoxy resin casting body at normal temperature and liquid nitrogen temperature (the test sample is soaked in liquid nitrogen for 10 min), and an open crack is adopted. Three point bend test specimens were tested according to ASTM D5045-90 standard, rectangular test specimens having the dimensions 90mm by 20mm by 5 mm. To prepare a three-point bending fracture toughness test piece, a 9mm deep notch was first cut at the center of the test piece with an HC-400 model digital display manual dicing saw, and then a 1mm deep crack was preformed at the end of the notch with a single-sided blade, and the length of the entire crack surface was observed with an optical microscope. The specimen span was 80mm and the loading rate was 2mm/min. Since the load-deformation curve of each specimen was linear before fracture, meaning a small yield near the crack tip, the fracture toughness, the critical stress intensity factor K, can be calculated for the experimental results using the linear elastic fracture mechanism IC As shown below
Wherein
P in the above formula Q Is the maximum load at break, S is the span, B is the specimen thickness, W is the specimen width, and α is the preformed crack length. At least six valid data specimens were tested for each content and the fracture toughness was then averaged and the results are shown in table 1.
TABLE 1
| Sample(s) | Comparative example 1 | Comparative example 2 | Example 4 | Example 5 | Example 6 |
| K IC | 0.4 | 0.6 | 1.5 | 1.8 | 2.1 |
Test example 2
And (3) impact performance test: in order to investigate the impact properties of the materials, the impact strength of the epoxy resin cast bodies was tested using an impact tester. Impact specimens were prepared in accordance with GB/T2571-95, with specimen dimensions of 80 mm. Times.10 mm. Times.4 mm. The impact test is carried out on an RG-30 type impact machine, and the maximum impact energy of an impact pendulum is 7.35J in the experiment. At least five valid samples were tested for each material. Low-temperature test conditions: the sample was immersed in liquid nitrogen for 10min, then quickly clamped onto the simple beam of the impact tester, the pendulum was released, and then the impact energy was recorded, the results are shown in table 2.
TABLE 2
| Sample (I) | Comparative example 1 | Comparative example 2 | Example 4 | Example 5 | Example 6 |
| Impact strength | 41.80 | 46.74 | 55.32 | 58.92 | 64.87 |
Test example 3
And (3) testing tensile property: the test was carried out using MZ-4000D material tensile tester (Jiangsu Mingzhu testing machines Co., ltd.) according to GB/T16584-1996, AL-7000M. The drawing speed was 500mm/min, and the results are shown in Table 3.
TABLE 3
| Sample (I) | Comparative example 1 | Comparative example 2 | Example 4 | Example 5 | Example 6 |
| Tensile strength | 31.8 | 40.1 | 55.4 | 62.8 | 69.9 |
| 100% ultimate strength | 7.9 | 8.2 | 8.8 | 9.5 | 9.8 |
As can be seen from table 1, the direct addition of the carbon nanotubes does not effectively improve the fracture toughness of the material, which may be because the added carbon nanotubes are agglomerated inside the polyurethane rubber, thereby failing to achieve the desired effect, while the fracture toughness of the modified high-strength nano rubber material is significantly improved;
as can be seen from table 2, the impact resistance of the modified high-strength nano rubber material is significantly enhanced;
from table 3, it can be seen that the 100% constant elongation and tensile strength of the modified high-strength nano rubber material obtain a reinforcing effect, and particularly, the tensile strength is increased by times.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (10)
1. The high-strength modified nano composite rubber material is characterized by comprising the following raw materials in parts by weight: 100 parts of polyurethane rubber, 50-60 parts of modified carbon nano tubes, 1-5 parts of zinc oxide, 0.5-3 parts of stearic acid, 0.5-1 part of accelerator and 0.5-1 part of additive.
2. The high-strength modified nanocomposite rubber material according to claim 1, wherein the method for producing the modified carbon nanotubes comprises the following steps:
charging dicyclohexylmethane diisocyanate and N, N-dimethylformamide into a container, magnetically stirring and heating to 50-60 ℃; slowly adding the hydroxylated multi-walled carbon nanotube suspension into a reaction vessel, dropwise adding dibutyltin dilaurate, and stirring and reacting at 50-60 ℃ for more than 8 hours; centrifuging the reacted mixture, washing the mixture for many times by using N, N-dimethylformamide, and washing away unreacted dicyclohexylmethane diisocyanate; and (3) putting the reactant into a vacuum oven at 40-60 ℃ for drying for more than 4h to obtain the modified carbon nano tube.
3. The high strength modified nanocomposite rubber material of claim 2, wherein said dibutyltin dilaurate is added in an amount of 3 to 4 drops per 8g dicyclohexylmethane diisocyanate.
4. The high strength modified nanocomposite rubber material of claim 2, wherein the ratio of dicyclohexylmethane diisocyanate to hydroxylated multiwalled carbon nanotube suspension is 8g:15mL-10g:15mL.
5. A high strength modified nanocomposite rubber material according to claim 2, wherein the temperature of said vacuum oven is set to 50 ℃.
6. The high-strength modified nanocomposite rubber material of claim 2, wherein the hydroxylated multi-walled carbon nanotube suspension is prepared by a method comprising the following steps:
putting a hydroxylated multi-walled carbon nanotube into a digestion tube, adding N, N-dimethylformamide, and dispersing under the action of ultrasound; the dosage ratio of the hydroxylated multi-walled carbon nanotube to the N, N-dimethylformamide is 100 mg: 25mLN, N-dimethylformamide.
7. The high strength modified nanocomposite rubber material of claim 1, wherein said accelerator is dimethylthiotoluenediamine.
8. The high strength modified nanocomposite rubber material of claim 1, wherein said additive is toluene diisocyanate.
9. A method for preparing a high-strength modified nanocomposite rubber material according to any one of claims 1 to 8, characterized by comprising the steps of:
s1: placing the polyurethane rubber in an open mill, thinly passing the polyurethane rubber to enable the rubber to have plasticity, and generating proper stacking rubber by adjusting a rubber baffle plate and a roller spacing; adding zinc oxide, and uniformly mixing the zinc oxide and the master batch by using a rubber tapping and rubber turning mode;
s2: adding the modified carbon nano tube, the accelerant, the additive and the stearic acid, and uniformly mixing the modified carbon nano tube, the accelerant, the additive and the stearic acid with the master batch in a rubber tapping and rubber turning mode;
s3: adjusting the roller distance to be small, further uniformly mixing the materials in a triangular packaging or rolling mode, thinly passing the materials for 6 to 8 times, and then discharging the materials;
s4: vulcanizing the obtained rubber by a flat vulcanizing instrument at the vulcanization temperature of 80-120 ℃, the vulcanization pressure of 20MPa and the vulcanization time of 45-75min, and putting the molded rubber into an oven for vulcanization to prepare the high-strength modified nano composite rubber material.
10. The method for preparing a high-strength modified nanocomposite rubber material according to claim 9, wherein the oven temperature is set at 100 ℃ and the drying time is 24 hours or more.
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