CN113603941A - Rubber composite material containing white carbon black and mixing method for reducing agglomeration of white carbon black in rubber matrix - Google Patents
Rubber composite material containing white carbon black and mixing method for reducing agglomeration of white carbon black in rubber matrix Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
- B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/005—Methods for mixing in batches
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/22—Component parts, details or accessories; Auxiliary operations
- B29B7/28—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control
- B29B7/286—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control measuring properties of the mixture, e.g. temperature, density
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/82—Heating or cooling
- B29B7/823—Temperature control
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/06—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
- B29B7/10—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary
- B29B7/18—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft
- B29B7/183—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft having a casing closely surrounding the rotors, e.g. of Banbury type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7466—Combinations of similar mixers
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Abstract
The invention provides a mixing method for reducing agglomeration of white carbon black in a rubber matrix, which comprises the following raw materials in parts by weight: raw rubber, white carbon black, silane coupling agent Si-69, N234 carbon black, accelerator DPG, rubber auxiliary agent and vulcanizing agent. The invention also provides a preparation method of the rubber composite material containing the white carbon black, and provides a mixing method for improving the agglomeration of the white carbon black in the rubber matrix, so that the problems of the agglomeration and secondary agglomeration of the white carbon black in the rubber matrix are solved, and the effect of modifying the surface of the white carbon black by using the silane coupling agent Si-69 is improved. Thereby improving the extrusion processing property of the rubber composite material with high content of white carbon black and improving the problem of low reinforcing efficiency of the white carbon black.
Description
Technical Field
The invention relates to the technical field of rubber, in particular to a rubber composite material containing white carbon black and a mixing method for reducing agglomeration of the white carbon black in a rubber matrix.
Background
With the rapid development of economy, the continuous improvement of the expressway network, the blowout-type growth of the automobile holding capacity and the inclination of policy guidance, the automobile industry continuously progresses worldwide. On one hand, environmental protection consciousness is continuously strengthened, and particularly, the relation of haze is particularly concerned about reducing automobile emission. On the other hand, the country gradually eliminates yellow-labeled vehicles and limits the sale of vehicles with substandard emission. Therefore, the tire should make its own contribution as the integration of the chassis of the automobile. The tire industry is in need of developing novel green and environment-friendly tires, realizing energy conservation and emission reduction of automobiles and reducing emission of harmful gases of the automobiles. Meanwhile, traffic safety regulations, environmental pollution worldwide and fuel shortage all put forward various index requirements on automobiles. Thus, the automobile industry puts higher demands on various indexes of the used tires.
One of the points of development of novel green and environment-friendly tires is to reduce the use of carbon black and use more environment-friendly white carbon black. The novel green and environment-friendly tire with low rolling resistance, wet skid resistance and excellent performance is developed, and the requirements of national low-carbon economy and green environment protection are met. Formula designers use a large amount of white carbon black instead of carbon black in the tire crown formula, so that the consumption of the white carbon black is increased. However, the possibility of the final complete replacement of carbon black by silica is not readily appreciated by the skilled person, mainly due to the limitations of the surface chemical properties of silica. A large number of hydroxyl groups exist on the surface of the white carbon black, and the hydroxyl groups have strong adsorption effect, so that the white carbon black is extremely easy to agglomerate, and a large number of formula workers begin to research the surface modification of the white carbon black and the emergence of a white carbon black surface modifier. For example, Xuqinghua and Xue Xiang Ju of Shandong Shanshu chemical engineering Co., Ltd are published in "Chinese rubber" 2017, No. 33, pages 43-44 "research on clean production process of vulcanization accelerator DPG", which is described in: the accelerator DPG can obviously accelerate the silanization reaction of the white carbon black and Si69, the Payne effect of the system is reduced, and the physical and mechanical properties of the rubber material are improved. The authors just describe that formulators tend to prefer to add accelerator DPG at the vulcanization stage, and there is no relevant application example for addition at the compounding stage.
The influence of accelerator DPG on the NR performance of white carbon black/carbon black composite filling is recorded in Chenyaoshao, Qiao Hui Jun, Liu Tao, Duei Hua and the like of Qingdao scientific university, which are published in No. 36 of Special rubber products 2015 in the text: under the condition of a certain amount of white carbon black/carbon black, the influence of the amine accelerator DPG on the mechanical property of NR is researched. The results show that the addition of DPG improves the dispersibility of the filler in NR and promotes the silylation reaction. With the increase of the dosage of DPG, the positive vulcanization time of the rubber material is shortened, the crosslinking density is increased, the wear resistance is improved, and the tensile strength and the aging resistance are slightly improved. However, in the sample preparation of the above technology, the accelerator DPG is added at the vulcanization stage and the above technology is only verified in the laboratory and is not verified in the industrial application.
At present, the method for improving the large-scale application of the white carbon black in the tire component rubber is to adjust a vulcanization system or use a silane coupling agent Si-69, and the dispersion of the white carbon black in a rubber matrix can be improved by selecting a proper silane coupling agent Si-69, so that the aim of improving various properties of the composite material of the white carbon black rubber is fulfilled. However, certain reaction conditions are needed for grafting the silane coupling agent Si-69 to the surface of the white carbon black, and the reaction conditions are harsh. The preparation method has certain limitation in the formulation design concept of factory production and multi-material combination, so that the effect of the silane coupling agent Si-69 modified white carbon black is greatly reduced. Formulators often improve the performance by increasing the proportion of the coupling agent, but the coupling agent easily causes scorching of the sizing material under a high-temperature environment, so that the sizing material loses the application capability. Formulators also propose that accelerator DPG can accelerate the silylation reaction, but all are in the laboratory stage and have not been implemented in the factory.
Accordingly, there is a need for improvements in the art.
Disclosure of Invention
The invention aims to solve the technical problem of providing an efficient mixing method for reducing the agglomeration of white carbon black in a rubber matrix.
In order to solve the technical problems, the invention provides a mixing method for reducing agglomeration of white carbon black in a rubber matrix, which comprises the following raw materials in parts by weight:
raw rubber: 100 parts of white carbon black: 40 parts, silane coupling agent Si-69: 4 parts, N234 carbon black: 11 parts, accelerator DPG: 0.3 part of rubber additive and vulcanizing agent.
As an improvement of the white carbon black-containing rubber composite material of the invention:
the rubber auxiliary agent comprises indirect zinc oxide: 3.5 parts, stearic acid: 1 part of an antioxidant 4020: 2 parts of an anti-aging agent RD: 1 part;
the vulcanizing agent comprises oil-filled sulfur: 0.51 part, accelerator NS: 1.7 parts;
as an improvement of the white carbon black-containing rubber composite material of the invention:
the crude rubber is natural rubber/neodymium cis-butyl rubber (B24).
The invention also provides a preparation method of the rubber composite material containing white carbon black, which comprises the following steps:
the first step is as follows: according to the mass ratio of the rubber composite material, adding raw rubber, N234 carbon black, white carbon black, a silane coupling agent Si-69, an accelerator DPG and a rubber auxiliary agent in the raw materials into an upper internal mixer of a series internal mixer for mixing;
the second step is that: when the pressure of the upper plug is 5MPa, the rotating speed is 45 r/min and the temperature reaches 115 ℃, the upper plug is lifted (so the temperature of the rubber material is lower and the rubber material does not need to be kept for a specific time);
the third step: pressing a top bolt, controlling the rotating speed to be 40 rpm, and starting constant temperature control when the temperature of the rubber material reaches 145 ℃;
the fourth step: the constant temperature is controlled for 20 seconds, the pressure of the upper top plug is kept at 5MPa, and the rotating speed is automatically adjusted between 10 and 20 revolutions per minute;
the fifth step: opening a discharge door, lifting a top bolt, and discharging the composite materials in the upper internal mixer to a lower internal mixer;
and a sixth step: the lower internal mixer receives the composite material, and the rotating speed is 20 revolutions per minute;
the seventh step: the lower internal mixer increases the rotating speed, the temperature of the composite material rises to 143 ℃, and the constant temperature control is started;
the rotating speed is intelligently controlled by adjusting the internal mixer according to the roll wrapping condition of the sizing material and the temperature of the sizing material.
Eighth step: and after the constant temperature control is carried out for 80 seconds, the discharging door is opened, and the rubber material is discharged to the lower auxiliary machine.
The ninth step: and the lower auxiliary machine receives the composite material, and performs addition and mixing of the vulcanizing agent, wherein the lower auxiliary machine is low-temperature one-step mixing. The process comprises the following steps:
the tenth step: and (6) tabletting and stacking the composite material.
The invention also provides a preparation method of the rubber composite material containing white carbon black, which comprises the following steps:
the first step is as follows: according to the mass ratio of the formula, raw rubber, N234 carbon black, white carbon black, a silane coupling agent Si-69 and common auxiliaries in the raw materials are added into an upper internal mixer of a series internal mixer for mixing;
the second step is that: mixing the upper top plug, lifting the upper top plug when the pressure of the upper top plug is 5MPa and the rotating speed is 45 turns and the temperature reaches 115 ℃;
the third step: pressing a top bolt, controlling the rotating speed to be 40 revolutions, and starting constant temperature control when the temperature of the rubber material reaches 145 ℃;
the fourth step: the constant temperature is controlled for 20 seconds, the pressure of the upper top bolt is kept at 5MPa, and the rotating speed is automatically adjusted from 50 percent of the rotating speed of the previous step to 10 revolutions;
the fifth step: opening a discharging door to lift an upper top bolt, and discharging the composite materials in the upper internal mixer to a lower internal mixer;
and a sixth step: the lower internal mixer receives the composite material, and the rotating speed is 20 revolutions;
the seventh step: the lower internal mixer automatically increases the rotating speed, the temperature of the composite material rises to 143 ℃, and the constant temperature control is started;
the rotating speed is intelligently controlled by adjusting the internal mixer according to the roll wrapping condition of the sizing material and the temperature of the sizing material.
Eighth step: and after the constant temperature control is carried out for 80 seconds, the discharging door is opened, and the rubber material is discharged to the lower auxiliary machine.
The ninth step: and the lower auxiliary machine receives the composite material, adds a vulcanizing agent and an accelerant DPG for mixing, and is a low-temperature one-time mixing method. The process comprises the following steps:
the tenth step: and (6) tabletting and stacking the composite material.
The rubber composite material containing white carbon black and the mixing method for reducing the agglomeration of the white carbon black in the rubber matrix have the technical advantages that:
the invention provides a mixing method for improving agglomeration of white carbon black in a rubber matrix, which solves the problems of agglomeration and secondary agglomeration of the white carbon black in the rubber matrix and improves the effect of modifying the surface of the white carbon black by a silane coupling agent Si-69. Thereby improving the extrusion processing property of the rubber composite material with high content of white carbon black and improving the problem of low reinforcing efficiency of the white carbon black. The invention can be used for agglomerating the white carbon black in the rubber matrix. The method can obtain the rubber composite material with better mechanical property and dynamic property than the traditional method, and the rubber composite material with high content of white carbon black can be applied to manufacturing crown rubber of the tire, thereby contributing to the development progress of green tires.
Compared with the traditional mixing method, the white carbon black-rubber composite material prepared by the invention has higher tearing strength, lower Akron abrasion, lower heat generation performance and relatively lower Payne effect among fillers, which is beneficial to the extrusion performance of the composite material and lower rolling resistance. The method of the invention not only enables the preparation method of the tire tread rubber with high proportion of white carbon black to be wider, reduces the risk of factory production of the high content white carbon black rubber composite material, but also provides conditions for the application of the tire tread rubber with high proportion of white carbon black.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1, a rubber composite material containing white carbon black is composed of the following raw materials in parts by weight:
raw rubber: 100 parts of white carbon black: 40 parts, silane coupling agent Si-69: 4 parts, N234 carbon black: 11 parts, accelerator DPG: 0.3 part of rubber additive and vulcanizing agent.
The rubber auxiliary agent comprises indirect zinc oxide: 3.5 parts, stearic acid: 1 part of an antioxidant 4020: 2 parts of an anti-aging agent RD: 1 part;
the vulcanizing agent comprises oil-filled sulfur: 0.51 part, accelerator NS: 1.7 parts;
the crude rubber is natural rubber/neodymium cis-butyl rubber (B24).
Relative to 100 parts by mass of raw rubber, the using amount of white carbon black is 40 parts, the using amount of N234 carbon black is 11 parts, the using amount of a silane coupling agent Si-69 is 10% of the using amount of the white carbon black, the using amount of an accelerator DPG is 0.3 part, the total using amount of common rubber auxiliaries is 10.5 parts, and the total using amount of a vulcanizing agent is 2.21 parts.
The common rubber auxiliary agents are conventional auxiliary agents used in the field of tire rubber, the dosage of the common rubber auxiliary agents is the conventional dosage of the field of tire rubber, the conventional auxiliary agents do not influence the trend of the test result of the invention, and other conventional dosages and varieties can be selected.
The vulcanizing agents used in the invention are all vulcanizing agents commonly used in the field of tire rubber, and the dosage of the vulcanizing agents is also the conventional dosage in the field of tire rubber; the N234 carbon black used in the invention is Kabot chemical Co., Ltd; the neodymium cis-butadiene rubber used in the invention is BRND40 from the Yanshan division of China petrochemical.
The accelerator DPG used in the present invention was a product of Shandong Shunhua chemical Co., Ltd, and the application part was 0.3 part. The accelerator DPG is chemically bis-guanidine and is offwhite powder, the initial melting point of the accelerator DPG is more than or equal to 145.0 ℃, and the molecular structure of the accelerator DPG is as follows:
the silane coupling agent Si-69 used in the invention is a product of Zhejiang metallocene rubber auxiliary products, and the application parts are 10 percent and 4 percent of white carbon black. The molecular structure is as follows:
the vulcanizing agent comprises oil-extended sulfur and an accelerator, and the accelerator is a sulfenamide accelerator.
The white carbon black has good low heat generation performance, but compared with carbon black, the white carbon black has the characteristic of high surface polarity due to a large amount of hydroxyl on the surface, and the white carbon black is easy to aggregate in the mixing and storage processes of the rubber composite material, so that various performances of the rubber composite material are reduced. In the rubber composite material containing the white carbon black, the silane coupling agent Si-69 is generally used for modifying the white carbon black so as to achieve the compatibility of the white carbon black and the rubber. The reaction between the hydroxyl on the surface of the white carbon black and the hydroxyl of the silane coupling agent Si-69 is the silanization reaction. In industrial production, a plurality of auxiliaries in the rubber composite material are often put into an internal mixer together for mixing, and hydroxyl on the surface of white carbon black has strong adsorption effect on the added auxiliaries, so that the silanization efficiency is reduced.
The invention adopts a method that the accelerator DPG and the white carbon black rubber matrix silane coupling agent Si-69 are put into the mixing at the sulfur-free mixing section together to improve the efficiency of the silanization reaction.
The detailed steps are as follows:
the first step is as follows: according to the mass ratio of the rubber composite material, adding raw rubber, N234 carbon black, white carbon black, a silane coupling agent Si-69, an accelerator DPG and a rubber auxiliary agent in the raw materials into an upper internal mixer of a series internal mixer for mixing;
the second step is that: when the pressure of the upper plug is 5MPa, the rotating speed is 45 r/min and the temperature reaches 115 ℃, the upper plug is lifted (so the temperature of the rubber material is lower and the rubber material does not need to be kept for a specific time);
the third step: pressing a top bolt, controlling the rotating speed to be 40 rpm, and starting constant temperature control when the temperature of the rubber material reaches 145 ℃;
the fourth step: the constant temperature is controlled for 20 seconds, the pressure of the upper top plug is kept at 5MPa, and the rotating speed is automatically adjusted between 10 and 20 revolutions per minute;
the fifth step: opening a discharge door, lifting a top bolt, and discharging the composite materials in the upper internal mixer to a lower internal mixer;
and a sixth step: the lower internal mixer receives the composite material, and the rotating speed is 20 revolutions per minute;
the seventh step: the lower internal mixer increases the rotating speed, the temperature of the composite material rises to 143 ℃, and the constant temperature control is started;
the rotating speed is intelligently controlled by adjusting the internal mixer according to the roll wrapping condition of the sizing material and the temperature of the sizing material.
Eighth step: and after the constant temperature control is carried out for 80 seconds, the discharging door is opened, and the rubber material is discharged to the lower auxiliary machine.
The ninth step: and the lower auxiliary machine receives the composite material, and performs addition and mixing of the vulcanizing agent, wherein the lower auxiliary machine is low-temperature one-step mixing. The process comprises the following steps:
the tenth step: and (6) tabletting and stacking the composite material.
Scheme II:
the first step is as follows: according to the mass ratio of the formula, raw rubber, N234 carbon black, white carbon black, a silane coupling agent Si-69 and common auxiliaries in the raw materials are added into an upper internal mixer of a series internal mixer for mixing;
the second step is that: mixing the upper top plug, lifting the upper top plug when the pressure of the upper top plug is 5MPa and the rotating speed is 45 turns and the temperature reaches 115 ℃;
the third step: pressing a top bolt, controlling the rotating speed to be 40 revolutions, and starting constant temperature control when the temperature of the rubber material reaches 145 ℃;
the fourth step: the constant temperature is controlled for 20 seconds, the pressure of the upper top bolt is kept at 5MPa, and the rotating speed is automatically adjusted from 50 percent of the rotating speed of the previous step to 10 revolutions;
the fifth step: opening a discharging door to lift an upper top bolt, and discharging the composite materials in the upper internal mixer to a lower internal mixer;
and a sixth step: the lower internal mixer receives the composite material, and the rotating speed is 20 revolutions;
the seventh step: the lower internal mixer automatically increases the rotating speed, the temperature of the composite material rises to 143 ℃, and the constant temperature control is started;
the rotating speed is intelligently controlled by adjusting the internal mixer according to the roll wrapping condition of the sizing material and the temperature of the sizing material.
Eighth step: and after the constant temperature control is carried out for 80 seconds, the discharging door is opened, and the rubber material is discharged to the lower auxiliary machine.
The ninth step: and the lower auxiliary machine receives the composite material, adds a vulcanizing agent and an accelerant DPG for mixing, and is a low-temperature one-time mixing method. The process comprises the following steps:
the tenth step: and (6) tabletting and stacking the composite material.
Test items
The rubber composite material prepared by mixing the scheme one and the scheme two is subjected to the following test items:
tensile strength, stress at definite elongation, elongation at break: the tensile rate is 500mm/min according to the tensile machine of WGJ-2500B of GB/T528-1998 Guilin Oaku electric appliance manufacturing Co., Ltd, and the detection results are shown in Table 1
Tear strength: the drawing was carried out using a square specimen in an electronic drawing machine of the GT-AI-7000S type in accordance with GB/T529-1999 at a drawing rate of 500 mm/min. The results are shown in Table 1.
Hardness of vulcanized rubber: measured on a Shore A hardness tester produced by Shanghai Risk mechanical plant according to GB/T531-1999. The results are shown in Table 1.
Compression heat generation: experiments were carried out according to GB1687-93 on a 3000E compression thermogenesis tester, manufactured by Beijing Youth electronics Co. The test sample is a cylinder with the height of 25mm and the diameter of 18mm, the experimental temperature is 55 ℃, the load is 55lb, the compression frequency is 30Hz, and the temperature rise and the deformation of the test sample in the compression process are tested. The results are shown in Table 1.
Attorney abrasion: the test is carried out on an Akron abrasion machine produced by high-speed railway science and technology Limited, the test method of the test is tested according to GB/T1689-1998, and the test principle of the method is that a test sample and a grinding wheel are rubbed under the action of a certain inclination angle and a certain load, and the abrasion volume or the abrasion index of the test sample in a certain mileage is measured. The test result is the volume abrasion, unit cm3/1.61km, when in test, pre-grinding is firstly carried out, the pre-grinding revolution is 795 revolutions, then the test is started, the test revolution is 3394 revolutions, two samples are tested for each kind of glue, and the test result is averaged. The results are shown in Table 1.
And DMA test: and testing the vulcanized rubber by dynamic mechanical analysis, wherein the test conditions are as follows: the test mode is a stretching mode, the frequency is 2.0Hz, the temperature range is-50-100 ℃, the dynamic strain is 0.25%, the static strain is 5%, and the heating rate is 2K/min. The results are shown in Table 1.
And (3) RPA test: the strain sweep conditions of the rubber compound were 60 ℃ x 1HZ, the temperature sweep conditions were 1HZ x 0.98%, the strain sweep conditions of the vulcanized rubber were 60 ℃ x 10HZ, the frequency sweep conditions were 60 ℃ x 10%, and the results of the measurements are shown in table 1.
And (3) rheological property testing: the test was carried out on a rheometer model MDR2000, manufactured by Shanghai Nuomegas instruments Ltd, according to the test method of the Standard GB/T16584-. The results are shown in Table 2.
TABLE 1 mechanical Property test results
TABLE 2 rheometer test results
| Scheme one | Scheme two | |
| MH | 20.67 | 20.68 |
| T10min | 3.96 | 3.42 |
| T90min | 12.47 | 12.29 |
| T5min | 26.67 | 25.46 |
As can be seen from the test results in tables 1 and 2, the rubber composite material obtained by mixing the accelerator DPG in the sulfur-free section by the mixing method of the present invention has superior properties of tear strength, Akron abrasion, heat generation, payne effect and rolling resistance.
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (5)
1. A rubber composite material containing white carbon black is characterized in that: the composite material is prepared from the following raw materials in parts by weight:
raw rubber: 100 parts of white carbon black: 40 parts, silane coupling agent Si-69: 4 parts, N234 carbon black: 11 parts, accelerator DPG: 0.3 part of rubber additive and vulcanizing agent.
2. The white carbon black-containing rubber composite material according to claim 1, wherein:
the rubber auxiliary agent comprises indirect zinc oxide: 3.5 parts, stearic acid: 1 part of an antioxidant 4020: 2 parts of an anti-aging agent RD: 1 part;
the vulcanizing agent comprises oil-filled sulfur: 0.51 part, accelerator NS: 1.7 parts.
3. The white carbon black-containing rubber composite material according to claim 2, wherein:
the crude rubber is natural rubber/neodymium cis-butyl rubber (B24).
4. A mixing method for reducing the agglomeration of white carbon black in a rubber matrix by using the rubber composite material containing white carbon black of any one of claims 1 to 3, wherein the mixing method comprises the following steps: the method comprises the following steps:
the first step is as follows: according to the mass ratio of the rubber composite material, adding raw rubber, N234 carbon black, white carbon black, a silane coupling agent Si-69, an accelerator DPG and a rubber auxiliary agent in the raw materials into an upper internal mixer of a series internal mixer for mixing;
the second step is that: mixing and lifting the upper top plug when the pressure of the upper top plug is 5MPa, the rotating speed is 45 revolutions per minute and the temperature reaches 115 ℃;
the third step: pressing a top bolt, controlling the rotating speed to be 40 rpm, and starting constant temperature control when the temperature of the rubber material reaches 145 ℃;
the fourth step: the constant temperature is controlled for 20 seconds, the pressure of the upper top plug is kept at 5MPa, and the rotating speed is automatically adjusted between 10 and 20 revolutions per minute;
the fifth step: opening a discharging door to lift an upper top bolt, and discharging the composite materials in the upper internal mixer to a lower internal mixer;
and a sixth step: the lower internal mixer receives the composite material, and the rotating speed is 20 revolutions per minute;
the seventh step: the lower internal mixer increases the rotating speed, the temperature of the composite material rises to 143 ℃, and the constant temperature control is started;
eighth step: after the constant temperature control is carried out for 80 seconds, a discharging door is opened, and the rubber material is discharged to a lower auxiliary machine;
the ninth step: the lower auxiliary machine receives the composite material, and adds and mixes vulcanizing agents;
the tenth step: and (6) tabletting and stacking the composite material.
5. A mixing method for reducing the agglomeration of white carbon black in a rubber matrix by using the rubber composite material containing white carbon black of any one of claims 1 to 3, wherein the mixing method comprises the following steps: the method comprises the following steps:
the first step is as follows: according to the mass ratio of the formula, raw rubber, N234 carbon black, white carbon black, a silane coupling agent Si-69 and common auxiliaries in the raw materials are added into an upper internal mixer of a series internal mixer for mixing;
the second step is that: mixing the upper top plug, lifting the upper top plug when the pressure of the upper top plug is 5MPa and the rotating speed is 45 turns and the temperature reaches 115 ℃;
the third step: pressing a top bolt, controlling the rotating speed to be 40 revolutions, and starting constant temperature control when the temperature of the rubber material reaches 145 ℃;
the fourth step: the constant temperature is controlled for 20 seconds, the pressure of the upper top bolt is kept at 5MPa, and the rotating speed is automatically adjusted from 50 percent of the rotating speed of the previous step to 10 revolutions;
the fifth step: opening a discharging door to lift an upper top bolt, and discharging the composite materials in the upper internal mixer to a lower internal mixer;
and a sixth step: the lower internal mixer receives the composite material, and the rotating speed is 20 revolutions;
the seventh step: the lower internal mixer automatically increases the rotating speed, the temperature of the composite material rises to 143 ℃, and the constant temperature control is started;
eighth step: after the constant temperature control is carried out for 80 seconds, a discharging door is opened, and the rubber material is discharged to a lower auxiliary machine;
the ninth step: the lower auxiliary machine receives the composite material, and adds a vulcanizing agent and an accelerant DPG for mixing;
the tenth step: and (6) tabletting and stacking the composite material.
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Address after: 311600 Xia Ya Zhen Chun Qiu Cun, Jiande City, Hangzhou City, Zhejiang Province Applicant after: Zhongce Rubber (Jiande) Co.,Ltd. Address before: 311600 Xia Ya Zhen Chun Qiu Cun, Jiande City, Huzhou City, Zhejiang Province Applicant before: Zhongce Rubber (Jiande) Co.,Ltd. |