Preparation method of modified rubber composition containing carbon black and carbon nano tubes
阅读说明：本技术 一种改性包含碳黑和碳纳米管的橡胶组合物的制备方法 (Preparation method of modified rubber composition containing carbon black and carbon nano tubes ) 是由 赛门索夫·尤里 卡特尔·尼古拉 伊万年科·叶卡捷琳娜 马合诺·斯塔尼斯拉夫 茹拉夫斯基·谢尔 于 2021-02-07 设计创作，主要内容包括：本发明涉及用于制备橡胶组合物的方法,具体公开了一种改性包含碳黑和碳纳米管的橡胶组合物的制备方法,根据以下方程式计算橡胶组合物中碳纳米管和碳黑的含量：m-(CNT)-碳纳米管含量,重量份；m-R-现有配方的橡胶含量,重量份；ρ-R-橡胶密度；S-(CNT)-碳纳米管的比表面积；d-(CNT)-碳纳米管的平均直径；-现有配方的碳黑含量,重量份；S-(CB)-碳黑的比表面积；m-(CB)-碳黑含量,重量份；之后分别在合适的溶剂中制备碳纳米管和碳黑的分散液,将所制备的分散液以计算的比例混合,干燥至恒重,并在混合机中使其松散,制备橡胶组合物,向其中加入碳黑与碳纳米管的预制混合物。本发明提升了拉升强度性能,并简化了橡胶组合物中碳纳米管和碳黑最佳含量的确定方法。(The invention relates to a method for preparing a rubber composition, and particularly discloses a method for preparing a modified rubber composition containing carbon black and carbon nanotubes, wherein the content of the carbon nanotubes and the carbon black in the rubber composition is calculated according to the following equation: m CNT -carbonNanotube content, parts by weight; m is R -rubber content of the existing formulation, parts by weight; rho R -rubber density; s CNT -specific surface area of carbon nanotubes; d CNT -the average diameter of the carbon nanotubes; -carbon black content of the existing formulation, parts by weight; s CB -specific surface area of carbon black; m is CB -carbon black content, parts by weight; then, dispersions of carbon nanotubes and carbon black are prepared in suitable solvents, respectively, the prepared dispersions are mixed in a calculated ratio, dried to a constant weight, and loosened in a mixer to prepare a rubber composition, to which a pre-prepared mixture of carbon black and carbon nanotubes is added. The invention improves the tensile strength performance and simplifies the determination method of the optimal content of the carbon nano tube and the carbon black in the rubber composition.)
1. A method for producing a modified rubber composition containing carbon black and carbon nanotubes, which comprises preliminarily preparing a mixture of carbon black and carbon nanotubes and introducing the mixture into a rubber composition, characterized in that the contents of carbon nanotubes and carbon black are determined by the following equation:
mCNT-carbon nanotube content, parts by weight;
mR-rubber content of the existing formulation, parts by weight;
ρR-rubber density;
SCNT-specific surface area of carbon nanotubes;
dCNT-the average diameter of the carbon nanotubes;
-carbon black content of the existing formulation, parts by weight;
SCB-specific surface area of carbon black;
mCB-carbon black content, parts by weight;
the mixture of carbon black and carbon nanotubes prepared is additionally loosened before being introduced into the rubber mixture.
Technical Field
The present invention is a process for the preparation of rubber compositions which are useful in the rubber industry.
Background
In recent years, carbon nanotubes have been used in rubber compositions together with carbon black, but the content ratio is often selected from several blending schemes. This method is very costly and does not always result in the optimum amounts of carbon nanotubes and carbon black in the rubber composition, which ensures high consumer performance of the rubber and rubber products produced.
There has been a method for preparing a rubber composition for use in the manufacture of molded rubber products, which is a white russian republic patent, patent No.: 17001, IPC C08L 9/02, C08K 13/02(2006.01), publication date 2013.04.30, the composition comprises the following components in parts by weight:
nitrile rubber
100
Sulfur
1.5-3.5
Thiazole 2MBS
1.0-3.0
Guanidine F
0.1-0.3
Zinc oxide
3.0-7.0
Industrial hard butter
0.1-2.0
Dibutyl sebacate
15.0-25.0
Carbon black P-803
100.0-150.0
Antioxidant Diafen FP
0.5-1.5
Coumarone-indene resins
1.0-3.0
Acetone P
1.0-3.0
Phthalic anhydride
0.5-2.0
Carbon nanotube
0.1-1.0
After the carbon nanotubes are introduced into the rubber composition, the tensile strength is increased from 12MPa to 12.2-12.5 MPa.
The reason for the lack of the expected technical result is that the mass contents of carbon nanotubes and carbon black in the rubber composition are not properly selected, resulting in insufficient tensile strength values.
There has been a method for producing a conductive rubber composition, see patents RU 2016145357(a), IPC B82B 3/00; C08L 101/00, publication date: 2018.05.22. a rubber composition was prepared according to this method, comprising the following components (unit: weight%) based on 100 parts by weight of rubber: 1.5-2.25 of sulfur; 1.0-2.0 parts of stearic acid; 3.0-5.0 parts of zinc oxide; sulfenamide T (TBBS) 0.7-1.0. The mixture of carbon black and multi-walled carbon nanotubes was added to the rubber composition in the following weight ratio (unit: parts by weight): 25.0-35.0 parts of conductive carbon black or 20.0-40.0 parts of non-conductive carbon black; 0.01-15.0 parts of multi-wall carbon nano-tube.
The reason for the lack of the expected technical result is insufficient tensile strength and stress value at 100% deformation.
There is a method for producing a rubber reinforced with a carbon material, see patent: CN107955224(a), IPC C08K 13/06; C08K 3/04; C08K 3/22; C08K 3/36; C08K 5/09; C08K 7/24; C08K 9/04; C08L 7/00; C08L 7/02; C08L 9/00, publication date: 2018.04.24. the method comprises the following steps: preparing aqueous dispersion containing carbon black carbon nano-tubes, graphene or graphene oxide, adding an affinity modifier, separating a solid phase and drying. The resulting composite filler is incorporated into a rubber composition. The incorporation of carbon nanotubes, graphene or graphene oxide into rubber compositions can improve the consumer performance of the rubber.
The reason for the lack of the expected technical result is that the mass contents of carbon nanotubes and carbon black in the rubber composition are not properly selected, resulting in moderate rubber consumption properties.
For the original rubber composition, the method of choice is "a method for preparing a rubber composition", see U.S. patent nos.: US2019322818(a1) IPC C01B 32/05; C01B 32/152; C01B 32/168; C01B 32/174; C08J 3/20; C08J 3/22; C08K 3/04; C08K 5/03; C09C 1/44; C09C 1/46; C09C 1/48; C09D 123/16, publication date: 2019.10.24. according to the method, firstly, carbon nano tubes and carbon black are suspended in a proper solvent, the prepared suspension is mixed and dried according to a certain proportion, then natural rubber with a certain mass is put into a Z-shaped laboratory stirrer and stirred to the concentration of viscous liquid, and then the mixture of the carbon black and the carbon nano tubes, a hardening agent, a coagulant, a plasticizer, an antioxidant and a retarder are mixed according to the following proportion (unit: parts by weight):
natural rubber Vistalon 706(EPM)
100
ZDMA coagulant
15
Plasticizer (Paraffin oil)
10
Antioxidant agent
1
Retarder
0.3
Hardening agent
5
Carbon black
50
Single wall carbon nanotube bundle
3.87
The reason for the lack of technical success is the insufficient tensile strength and stress value at 10% deformation.
Disclosure of Invention
The invention of the present invention is based on the following problems: according to the preliminary calculation, the contents of carbon black and carbon nanotubes in the rubber composition are changed, thereby increasing the tensile strength characteristics of the rubber composition while simplifying the determination method of the optimum contents of carbon nanotubes and carbon black in the rubber composition.
This problem is solved by a process for the preparation of a modified rubber composition containing carbon black and carbon nanotubes, which comprises preparing in advance a mixture of carbon black and carbon nanotubes and introducing the mixture into a rubber composition prepared according to the inventive process, the contents of carbon nanotubes and carbon black being calculated according to the following formula:
mCNT-carbon nanotube content, parts by weight;
mR-rubber content of the existing formulation, parts by weight;
ρR-rubber density;
SCNT-specific surface area of carbon nanotubes;
dCNT-the average diameter of the carbon nanotubes;
-carbon black content of the existing formulation, parts by weight;
SCB-specific surface area of carbon black;
mCB-carbon black content, parts by weight;
the mixture of carbon black and carbon nanotubes prepared is additionally loosened before being introduced into the rubber mixture.
The technical result of the invention is to improve the tensile strength performance and simplify the determination method of the optimal content of the carbon nano tube and the carbon black in the rubber composition.
Detailed Description
The method of the invention is carried out by the following steps:
ASTM D1765N 550 carbon black;
ASTM D1765N 220 carbon black;
ASTM D1765N 330 carbon black;
TU 24.1-03291669-: 2009 carbon nanotubes;
carbon nanotubes manufactured by Sunnatech, Inc.;
vistalon 706(EPM) natural rubber;
acrylonitrile and butadiene copolymer NBR 3365;
natural rubber SMR 20;
natural rubber SMR L;
industrial zinc oxide (vulcanizing agent);
stearic acid ASTM 1801;
ASTM antioxidant N-isopropyl-N-phenylenediamine IPPD;
ASTM 935P mold release agent;
DOP plasticizer;
sulphur sulfide powder (Sigma-Aldrich), purity 98.5%;
CBS N-cyclohexyl-2-benzothiazole sulfenamide;
TMTD tetramethylthiuram disulfide, accelerator;
14 ° ethanol GOST 10748.1: 2008.
the preparation of the rubber composition requires:
a Brenbury Z-blender;
a Bridge two-roll blender;
a hot-pressing forming machine;
a UZDN-M900T ultrasonic disperser;
waring 8.8A012 high-speed stirrer;
2167P50 tensile tester;
testometric MT350 tensile tester.
The method of the invention operates as follows: the carbon nanotube and carbon black content of the rubber composition is first calculated. For this purpose, the following values are assigned to the following equations: the rubber density, the specific surface area of the carbon nano tube, the average diameter of the carbon nano tube, the specific surface area of the carbon black and the content of the carbon black in the existing formula.
mCNT-carbon nanotube content, parts by weight;
mR-rubber content of the existing formulation, parts by weight;
ρR-rubber density;
SCNT-specific surface area of carbon nanotubes;
dCNT-the average diameter of the carbon nanotubes;
-carbon black content of the existing formulation, parts by weight;
SCB-specific surface area of carbon black;
mCB-carbon black content, parts by weight;
samples of rubber compositions containing carbon nanotubes and carbon black were then prepared and the amounts determined by calculation. Dispersions of carbon nanotubes and carbon black were prepared separately using an ultrasonic disperser, the prepared dispersions were mixed in the calculated ratio and additionally subjected to ultrasonic treatment in an UZDN-M900T ultrasonic disperser, dried to constant weight, and then loosened in a blender. The rubber base material is filled into a Brenbury Z-shaped stirrer, industrial zinc oxide, stearic acid, an antioxidant, an ASTM 935P antisticking agent and sulfur powder are added and mixed, and the stirring is continued for 4 to 6 minutes. Then, the pre-prepared mixture of carbon black and carbon nanotubes and the plasticizer dibutyl phthalate were added and stirring was continued for 2-5 minutes. The resulting mixture was removed and cooled to a temperature below 110 ℃ before CBS N-cyclohexyl-2-benzothiazole sulfenamide, TMTD tetramethylthiuram disulfide were added to the mill and stirred until homogeneous. The resulting mixture is left at room temperature for 8-24 hours and vulcanized at a pressure of 12-18MPa and a temperature of 140-160 ℃. Vulcanization was carried out in a mold capable of preparing samples suitable for measuring the mechanical properties of the resulting rubber composition, the samples being used for determination of ultimate tensile strength, strain at break, 10% and 100% deformation stress.
Whether the technical achievement is achieved is confirmed through a specific implementation example.
Example 1
The content of the carbon nano tube of the modified composition in the method is calculated according to the following formula (1)
Wherein:
mRthe rubber content of the existing formula is as follows: 100g of the total weight of the mixture;
ρRrubber density: 0.86g/cm3；
dCNTAverage diameter of carbon nanotube: 6 nm;
SCBcarbon blackSpecific surface area of (2): 42m2/g；
SCNTSpecific surface area of carbon nanotube: 1300m2/g；
The carbon black content of the existing formula is as follows: 60g of the total weight of the mixture;
the amount of carbon nanotubes added can be calculated according to equation (1):
the content of carbon black is calculated according to the formula (2):
dispersions of carbon nanotubes and carbon black were prepared separately. The specific surface area of 11g was about 1300m2Putting the carbon nano-tube in per gram into a feed chute of an UZDN-M900T ultrasonic disperser, gradually adding 550 ml of ethanol while continuously stirring, and ultrasonically homogenizing for 20 minutes. A dispersion of 120 g of ASTM D1765N 550 carbon black (specific surface area about 42m2/g) and 550 ml of ethanol was prepared in a similar manner. The prepared dispersions were mixed in the same volume ratio, giving a weight ratio of 5.4: 60 carbon nanotubes and carbon black. The mixture was additionally sonicated in a UZDN-M900T ultrasonic disperser, dried to constant weight, and fluffed in a blender. 1000g of Vistalon 706(EPM) natural rubber was charged in a Brenbury Z blender and mixed with 150g of ZDMA coagulant, 10g of antioxidant, 3g of retarder with continuous stirring for 6 minutes, after which 654g of a pre-mix of carbon black and carbon nanotubes, 100g of paraffin oil plasticizer and stirring was continued for 5 minutes. The resulting mixture was removed and cooled to 80 ℃. Then 50g of hardener was added to the mill and stirred until homogeneous. The resulting mixture was left at room temperature for 12 hours and vulcanized at a pressure of 15MPa and a temperature of 150 ℃. Is vulcanized inCan be carried out in a sample mold capable of preparing a mold suitable for measuring the mechanical properties of the resulting rubber composition, and the sample is used for determining the ultimate tensile strength, the strain at break, and the 10% deformation stress. The rubber composition samples produced had the following tensile properties:
ultimate strength (sigma) -23.2 MPa;
strain at break (. epsilon. -425%);
stress (. epsilon.10%) at 10% deformation-1.8 MPa.
Examples 2 to 6
A rubber composition was prepared as in example 1, except that the carbon black grade and the content of carbon nanotubes were used, and the diameter value of carbon nanotubes was set within an acceptable range for the purpose of calculation. The rubber compositions of examples 2 to 6 had the compositions shown in Table 1, and the results of measurement of ultimate tensile strength, strain at break and stress at 10% strain were shown in Table 2.
TABLE 1
The rubber composition taking natural rubber Vistalon 706 as a base material comprises the following components in parts by weight:
rubber density of 0.86g/cm3The specific surface area of the carbon nanotube was 1300m2Specific surface area of N550 carbon black 42m2The specific surface area of N220 carbon black (trade name N220) is 120m2/g。
TABLE 2
Characteristics of the rubber composition based on Vistalon 706 rubber:
rubber density of 0.86g/cm3The specific surface area of the carbon nanotube was 1300m2Specific surface area of N550 carbon black 42m2The specific surface area of N220 carbon black (trade name N220) is 120m2/g。
Examples 7n and 8n are the ingredients and properties of the original rubber composition and are the existing compositions modified according to the process. The cited data confirm the technical success of the rubber compositions based on natural rubber: the ultimate strength (sigma) is increased by 0.9-8.3 MPa.
Examples 9 to 11
A rubber composition was prepared as in example 1, except that the base material of the composition was a synthetic copolymer of acrylonitrile NBR 3365, TU 24.1-03291669-A009: 2009 multiwall carbon nanotubes and varying their content, N550 carbon black was used, and the specific surface area value thereof was varied in the calculation. The rubber compositions are shown in examples 9 to 11 in Table 3, and the results of measuring the ultimate tensile strength, strain at break and stress at 100% strain are shown in examples 9 to 11 in Table 4.
TABLE 3
The rubber composition using the synthetic acrylonitrile copolymer NBR 3365 as the base material comprises the following components in parts by weight:
TABLE 4
Characteristics of the rubber composition based on the synthetic acrylonitrile copolymer NBR 3365:
the rubber density is 0.915g/cm3The specific surface area of the carbon nanotube is 230m2G, average diameter of carbon nanotubes: 15 nm.
Example 12
The ingredients and properties of the rubber compositions prepared according to the standard formulation of Ningbo Tashun sealing technology, Inc. (http:// www.taisun-sealing. com /) were the original compositions modified according to the process. The cited data confirm the technical success of the rubber compositions based on synthetic rubbers: the ultimate strength (sigma) is increased by 0.4-1.9MPa, the breaking strain (epsilon) is increased by 50-154%, and the stress (epsilon 100%) at 100% deformation is increased by 0.8-2.3 MPa. The above examples also confirm the correctness of the calculation of the rubber composition ingredients: in order to optimize the ingredients of the rubber composition, it is necessary to additionally introduce carbon nanotubes without substantially changing the content of carbon black.
Examples 13 to 18
A rubber composition was prepared as in example 1, except that the base stock of the composition was natural rubber SMR 20 and SMR L, and TU 24.1-03291669-: 2009 multi-walled carbon nanotubes and carbon nanotubes produced by Sunnanotech ltd, and varying the content thereof, and using carbon black and modifying the specific surface area value thereof in the calculation. The rubber compositions are shown in Table 5, examples 13 to 18, and the results of measuring the ultimate tensile strength, strain at break and stress at 10% strain are shown in Table 6, examples 13 to 18. Example 19b ingredients and Properties of the base rubber composition, the formulation is from: evghenii Harea, RadekLiudamia Storozhuk, Yurii Sementsov, Nikolai Kartel.Stude of tertiary properties of tertiary rubber containing carbon nanotubes and carbon black as hybrid filters// Applied nanosciences https:// doi.org/10.1007/s 13204-018-. Example 20b ingredients and Properties of the base rubber composition, the formulation is from: i mail.A.F.ramly.and N.Othman.the Effect of Carbon Black/Multi wall Carbon Nanotube hybrids on the Properties of Natural Rubber Nanocomposites// Polymer-Plastics Technology and engineering.50:660-666.2011. The rubber composition prepared according to the above formulation is the original composition modified according to the present method.
TABLE 5
Rubber composition based on SMR and SMR L Natural rubber (parts by weight):
density of rubber ═0.86g/cm3The specific surface area of the carbon nanotube is 230m2The average diameter of carbon nanotubes (TU 24.1-03291669-.
TABLE 6
Properties of rubber compositions based on SMR and SMR L Natural rubber:
rubber density of 0.86g/cm3The specific surface area of the carbon nanotube is 230m2The average diameter of carbon nanotubes (TU 24.1-03291669-.
The cited data demonstrate the technical success achieved with rubber compositions based on natural and synthetic rubbers.
The method can be used for standard equipment of rubber industry enterprises, and does not increase additional cost obviously.
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