CN117565258A - Mixing method for improving filler dispersion effect in rubber composition - Google Patents
Mixing method for improving filler dispersion effect in rubber composition Download PDFInfo
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- CN117565258A CN117565258A CN202311234293.5A CN202311234293A CN117565258A CN 117565258 A CN117565258 A CN 117565258A CN 202311234293 A CN202311234293 A CN 202311234293A CN 117565258 A CN117565258 A CN 117565258A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 98
- 239000005060 rubber Substances 0.000 title claims abstract description 98
- 238000002156 mixing Methods 0.000 title claims abstract description 49
- 239000000945 filler Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000006185 dispersion Substances 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 title claims abstract description 29
- 230000000694 effects Effects 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000006229 carbon black Substances 0.000 claims description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 238000004513 sizing Methods 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 9
- 239000005062 Polybutadiene Substances 0.000 claims description 8
- 230000003712 anti-aging effect Effects 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229920002857 polybutadiene Polymers 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- 244000043261 Hevea brasiliensis Species 0.000 claims description 7
- 229920003052 natural elastomer Polymers 0.000 claims description 7
- 229920001194 natural rubber Polymers 0.000 claims description 7
- 239000012190 activator Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 5
- 229920002943 EPDM rubber Polymers 0.000 claims description 4
- 229920000459 Nitrile rubber Polymers 0.000 claims description 4
- 229920005683 SIBR Polymers 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 4
- 238000010057 rubber processing Methods 0.000 claims description 4
- 239000011163 secondary particle Substances 0.000 claims description 4
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims 9
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 229920003049 isoprene rubber Polymers 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 10
- 238000005299 abrasion Methods 0.000 abstract description 9
- 230000001965 increasing effect Effects 0.000 abstract description 9
- 230000032683 aging Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000004636 vulcanized rubber Substances 0.000 description 7
- 230000000930 thermomechanical effect Effects 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 230000020169 heat generation Effects 0.000 description 4
- 239000012779 reinforcing material Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- -1 fatty acid zinc salt Chemical class 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000004200 microcrystalline wax Substances 0.000 description 2
- 235000019808 microcrystalline wax Nutrition 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000003878 thermal aging Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 241000220433 Albizia Species 0.000 description 1
- 241000227425 Pieris rapae crucivora Species 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- 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
- C08L9/06—Copolymers with styrene
-
- 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
- B29B7/7461—Combinations of dissimilar mixers
-
- 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
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the application field of industries such as tires, products and the like, and relates to a mixing method for improving the dispersion effect of filler in a rubber composition. A mixing method for improving the dispersing effect of filler in rubber composition features that the filler and processing aid are put in an internal mixer, the rotor is rotated to stir them, the speed of rotor in internal mixer is controlled to 40-60rpm, and the stirring is carried out for 50-200s, and then the rubber component is added for mixing. Compared with the traditional mixing process, the physical property, abrasion performance and dynamic performance of the rubber material are improved to a certain extent under the earlier stage of not increasing the cost of the formula materials.
Description
Technical Field
The invention belongs to the application field of industries such as tires, products and the like, and relates to a mixing method for improving the dispersion effect of filler in a rubber composition.
Background
In the rubber tire industry, the main stream reinforcing materials of rubber are divided into two main types, carbon black and white carbon black. It is well known that the degree of dispersion of the reinforcing material determines the mechanical properties of the mix, such as the abrasion properties of the mix, the more uniform the dispersion of the reinforcing material in the rubber, the more excellent the abrasion properties of the mix.
In order to promote the dispersion of the reinforcing material in the rubber, a certain amount of silane coupling agent is used for changing the surface polarity of the white carbon black according to the use proportion of the white carbon black, so that the surface of the white carbon black is changed from polarity to non-polarity which is the same as that of the rubber, and the dispersion difficulty of the white carbon black is reduced. Meanwhile, substances such as rubber operating oil, fatty acid zinc salt dispersing agents and the like are used for enhancing the dispersion of the filler, and the mechanism is to increase the lubrication of the surface of the filler, reduce the friction between the filler and the rubber and further increase the dispersibility of the filler. Since carbon black is a nonpolar material and is the same as rubber, it is not necessary to modify carbon black by using a silane coupling agent, but it is also possible to use a rubber processing oil, a fatty acid zinc salt-based dispersing agent or the like to enhance the dispersion of the filler, and the mechanism is the same as that of the white carbon black filler. Since the silane coupling agent, the rubber processing oil and the fatty acid zinc salt-based dispersing agent all function to enhance the filler dispersion, these are hereinafter collectively referred to as processing aids.
The processing aid used in the rubber compound is mostly liquid and is soaked and adsorbed by the filler in the internal mixer, but the processing aid is used in a small amount (the silane coupling agent in the general white carbon black formula is 8.0-12.0% of the white carbon black, the zinc salt type dispersing agent of the fatty acid is not more than 5phr, and the rubber operating oil is regulated according to the hardness of the formula) relative to the filler with a large amount (generally 60phr to 100phr, even up to 140phr of white carbon black is used in the partial high-filling formula), so that only a small part of the filler is soaked in the processing aid. When the rubber and the processing aid enter the mixing stage, the processing aid enters the rubber with the infiltrated filler, after which the dispersion medium of the processing aid becomes a solid-phase compound, dispersion becomes difficult, and therefore the probability of the non-infiltrated filler coming into contact with the processing aid decreases, and the degree of dispersion of the non-infiltrated filler in this portion decreases.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a mixing method for improving the dispersion effect of filler in a rubber composition, which is characterized in that filler, processing aid and the like are pre-dispersed in an internal mixer in advance, various substances are uniformly dispersed, and then rubber is added, so that the contact reaction probability of the filler and the processing aid is increased, and the dispersibility of the filler is increased.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a mixing method for improving the dispersing effect of filler in rubber composition features that the filler and processing aid are put in an internal mixer, the rotor is rotated to stir them, the speed of rotor in internal mixer is controlled to 40-60rpm, and the stirring is carried out for 30-200s, and then the rubber component is added for mixing.
Preferably, the rubber component includes one or more of isoprene-based rubber, polybutadiene rubber (BR), styrene-butadiene rubber (SBR), styrene-isoprene-butadiene rubber (SIBR), ethylene-propylene-diene rubber (EPDM), chloroprene Rubber (CR), and nitrile rubber (NBR). Examples of isoprene-based rubbers include Natural Rubber (NR), polyisoprene rubber (IR), modified NR, and modified IR. NR may be one commonly used in the tire industry, such as SIR20, RSS #3 or TSR20; IR may be one commonly used in the tire industry, such as IR2200.
Preferably, the filler comprises one or two of carbon black and white carbon black. The white carbon black referred to in the invention is common white carbon black, high-dispersion white carbon black and the like produced by processes such as a precipitation method, a gas phase method and the like. The carbon black is carbon black obtained by a furnace method, a channel method, a thermal cracking method, etc. Preferably, the BET specific surface area of the carbon black particles is 20 to 160m2/g, more preferably 40 to 130m2/g, still more preferably 50 to 120m2/g; the average secondary particle diameter of the carbon black particles is preferably 0.05 to 3. Mu.m, more preferably 0.1 to 1.0. Mu.m, still more preferably 0.2 to 0.9. Mu.m; most preferably, the carbon black is one or more of N134, N220, N234, N330, N375, N550; preferably, the BET specific surface area of the white carbon black is 50 to 250m 2 Preferably from 80 to 210m2/g, more preferably from 100 to 190m2/g; the average secondary particle diameter of the white carbon black is preferably 0.04 to 3. Mu.m, more preferably 0.1 to 1. Mu.m, and still more preferably 0.2 to 0.7. Mu.m.
Preferably, the processing aid comprises one or two of a silane coupling agent, a dispersing resin, a rubber processing oil, an activator and an anti-aging agent.
Preferably, the rubber composition is prepared by mixing the following raw materials in parts by weight based on 100 parts by weight of the rubber component:
100 parts of rubber component
70-120 parts of white carbon black
0-20 parts of carbon black
Silane coupling agent 5.0-10.0 parts
8.0-15.0 parts of rubber operating oil;
and proper amount of activator, anti-aging agent, sulfur and promoter.
Preferably, the rubber component is 65-80 parts of solution polymerized styrene-butadiene rubber and 20-35 parts of cis-butadiene rubber.
Preferably, the method comprises the steps of:
1. the upper auxiliary machine process comprises the following steps:
(1) controlling the rotor speed of an internal mixer to be 40-60rpm, controlling the pressure of a top plug to be 50-60N/cm < 2 >, adding all raw materials except rubber, including white carbon black, a silane coupling agent, rubber operating oil and other chemical additives, lowering the top plug, and keeping the preset time to be 50-200s;
(2) lifting the top bolt and adding rubber;
(3) lowering the top bolt to raise the temperature of the rubber material to 80-120 ℃;
(4) lifting the top bolt and keeping for 4-8s;
(5) lowering the top bolt to raise the temperature of the rubber material to 140-150 ℃, keeping the temperature of the rubber material constant at 145+/-2 ℃ by controlling the rotating speed, and mixing for 100-130s;
(6) discharging the sizing material to a lower auxiliary machine;
2. the process of the auxiliary machine comprises the following steps:
(1) heating the sizing material to 140-150 ℃;
(2) mixing at 145+/-2 ℃ for 250-400s;
(3) discharging glue to an open mill: turning over the cooled sizing material to 90-100 ℃, adding sulfur and an accelerator on an open mill for uniform dispersion, and cooling the lower piece to room temperature.
Preferably, the rubber composition is prepared by mixing the following raw materials in parts by weight based on 100 parts by weight of the rubber component:
100 parts of rubber component
40-60 parts of carbon black
2.0 to 5.0 parts of dispersion resin
3.0-10.0 parts of rubber operating oil;
and proper amount of activator, anti-aging agent, sulfur and promoter.
Preferably, the rubber component is 30-50 parts of natural rubber; 50-70 parts of cis butadiene rubber.
Preferably, the mixing of the rubber material in the method is carried out in two stages, wherein one stage is carried out in a shearing type internal mixer; the two sections are mixed on a double-roller open mill, and the specific mixing process of each section is as follows:
and (3) mixing: the rotating speed of the rotor is 40-60rpm per minute; adding all raw materials except rubber, including carbon black, rubber operating oil and other chemical additives, lowering a top bolt, and keeping the preset time for 50-200s; rubber is added into the upper ram, the upper ram is lowered, the temperature of the internal mixer is raised to 120-140 ℃, and the upper ram is lifted once to sweep. Raising the temperature of the internal mixer to 140-160 ℃ and discharging glue;
two-stage mixing: uniformly mixing on a master batch roller, adding a sulfur and an accelerator, and cutting for 3-4 times respectively; and (5) manually and alternately rolling and wrapping the sheet by a triangular bag for 4-6 times, and cooling to room temperature.
According to the technical scheme, the filler, the processing aid and the like are firstly put into the internal mixer in the mixing stage, then the rotor rotates to stir the filler, the processing aid and the like, after full stirring, the immersed filler and the filler which is not immersed are fully and uniformly mixed, rubber is added, at the moment, in the rubber compound, the non-immersed filler is shortened at equal intervals with the immersed filler and the processing aid, the contact reaction rate of the filler and the processing aid is increased, so that the dispersibility of the filler is increased, and finally, the performances of the rubber compound are improved. Compared with the traditional mixing process, the physical property, abrasion performance and dynamic performance of the rubber material are improved to a certain extent under the earlier stage of not increasing the cost of the formula materials.
Drawings
FIG. 1 is a schematic diagram of the mixing principle of the present invention.
Detailed Description
The technical scheme in the embodiment of the invention is checked and fully described in combination with the embodiment of the invention, and the invention is further explained. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. Given the embodiments of the present invention, all other embodiments that would be obvious to one of ordinary skill in the art without making any inventive effort are within the scope of the present invention.
Example 1
The formulation of example 1 is specifically shown in table 1 (parts by weight).
Table 1 example 1 formulation details
| Example 1 series | |
| Solution polymerized styrene-butadiene rubber 1 | 96.25 |
| Cis butadiene rubber x 2 | 30.00 |
| White carbon black 3 | 80.00 |
| Silane coupling agent 4 | 6.40 |
| Rubber operating oil 5 | 10.00 |
| Others 6 | 11.90 |
| Totals to | 234.55 |
Table 1 footnotes
*1:2438-2HM, an Albizzia chemical product;
*2: BR9000, daqing petrochemical;
*3:1165MP, a sor-vitamin chemical product;
*4: si69, jiangxi Hongbai New Material Co., ltd;
*5: v700, ningbo Hansheng Co., ltd;
*6: comprises 2.0 parts of zinc oxide, 2.0 parts of stearic acid, 3.0 parts of anti-aging agent, 1.0 parts of microcrystalline wax, 1.5 parts of sulfur, 1.0 part of accelerator and the like, which are all commercial industrial grade products.
Serial sample preparation: (the process uses a series-type internal mixer
Controlling the rotor speed of the internal mixer to be 40-60rpm, the upper ram pressure to be 50-60N/cm < 2 >, and the cooling water temperature of the internal mixer to be 30-40 ℃, wherein the method comprises the following steps:
1. the upper auxiliary machine process comprises the following steps:
(1) adding all raw materials except rubber, including white carbon black, a silane coupling agent, rubber operating oil and other chemical additives, lowering a top plug, and keeping for a preset time (the preset time is shown in Table 2);
(2) lifting the top bolt and adding rubber;
(3) lowering the top bolt to raise the temperature of the sizing material to 100 ℃;
(4) lifting the top plug, holding 5 ";
(5) lowering the top bolt to raise the temperature of the rubber material to 145 ℃, keeping the temperature of the rubber material constant at 145+/-2 ℃ by controlling the rotating speed, and mixing for 120';
(6) discharging the sizing material to a lower auxiliary machine.
2. The process of the auxiliary machine comprises the following steps:
(1) heating the sizing material to 145 ℃;
(2) mixing at a constant temperature of 145+/-2 ℃ for 300';
(3) discharging glue to an open mill: turning over the cooled sizing material to 90-100 ℃, adding sulfur and a vulcanization accelerator on an open mill for uniform dispersion, and cooling the lower piece to room temperature.
TABLE 2 example 1 series of mixing hold times
| Examples 1 to 0 | Examples 1 to 30 | Examples 1 to 60 | Examples 1 to 90 | Examples 1 to 120 | |
| Mixing hold time/sec | 0 | 30 | 60 | 90 | 120 |
Test method for evaluating rubber properties
Physical properties:
the hardness at room temperature was measured based on GB/T531.1-2008, and the results are shown in Table 3, the higher the value, the higher the hardness.
The tensile strength measured based on GB/T528-2009 is shown as "tensile strength". In addition, the elongation at break during the same test is shown as "elongation at break". The product of tensile strength and elongation at break is shown as the "tensile product" as shown in table 3. The larger the value, the higher the reinforcing property, and the better the physical properties. The aging condition of the physical properties after aging is 100 ℃ for 48 hours, the ratio of the tensile product after aging to the tensile product before aging is the thermal aging retention rate, and the larger the value is, the better the aging resistance is.
Abrasion resistance-Akron abrasion:
the acle abrasion measured based on GB/T1689-2014 was shown to be "acle abrasion", and the results are shown in table 3. The smaller the value, the less wear and the better the wear resistance.
Dynamic performance-dynamic thermo-mechanical analysis (Dynamic thermomechanical analysis, DMA):
measured using a dynamic thermo-mechanical analyzer of the VR-7120 type manufactured by UESHIMA corporation, japan. The test conditions were: a stretch mode; frequency, 12Hz; strain, 7% ± 0.25%; temperature rise is 2 ℃/min. The results are shown in Table 3. The tan delta value at 0 ℃ characterizes the wet grip of the vulcanized rubber, the greater the value, the better the wet grip of the vulcanized rubber to make a tire; the tan delta value at 60 ℃ characterizes the hysteresis loss of the vulcanized rubber, the smaller the value, the lower the hysteresis loss of the vulcanized rubber, and the lower the rolling resistance of the resulting tire.
TABLE 3 series of test results for example 1
As can be seen from comparing the series of data in example 1, as the white carbon black and the processing aid are pre-dispersed in the internal mixer, the longer the mixing time is, the more excellent the physical properties of the rubber material are, the better the abrasion performance is, and the more excellent the dynamic performance is, the more the wet skid resistance is increased, and the rolling resistance is reduced.
A batch of 235/45R18 gauge tires was made using the compounds of examples 1-0 and examples 1-120 and tested for full tire, the test results being shown in Table 4.
Table 4 test tire machine performance data for examples 1-0 and 1-120 compounds
From the data in Table 4, it can be seen that the high speed and durability of the tire prepared by the invention meet the requirements of the regulations, and the wet skid resistance and rolling resistance of the tire are improved to some extent.
Example 2
The series of formulations of example 2 are specifically shown in table 5 (parts by weight).
TABLE 5 example 2 formulation details
| Example 2 series | |
| Natural rubber 1 | 40.00 |
| Cis butadiene rubber x 2 | 60.00 |
| Carbon black 3 | 50.00 |
| Dispersing resin 4 | 3.00 |
| Rubber operating oil 5 | 5.00 |
| Others 6 | 10.50 |
| Totals to | 168.50 |
Table 5 footnotes
*1: SVR 3L, vietnam product;
*2: BR9000, daqing petrochemical;
*3: n550, cabot chemical products;
*4: si69, jiangxi Hongbai New Material Co., ltd;
*5: v700, ningbo Hansheng Co., ltd;
*6: comprises 2.0 parts of zinc oxide, 2.0 parts of stearic acid, 3.0 parts of anti-aging agent, 1.0 parts of microcrystalline wax, 1.5 parts of sulfur, 1.0 part of accelerator and the like, which are all commercial industrial grade products.
Example 2 series sample preparation:
the mixing of the rubber is carried out in two stages, one of which is carried out in a shear-type internal mixer. The two sections are mixed on a double-roller open mill, and the specific mixing process of each section is as follows:
and (3) mixing: the rotor speed was 50rpm per minute. Adding all raw materials except rubber, including carbon black, rubber operating oil and other chemical additives, lowering a top plug, and keeping for a preset time (the preset time is shown in Table 6); rubber is added into the upper ram, the upper ram is lowered, the temperature of the internal mixer is raised to 130 ℃, and the upper ram is lifted once to sweep. The temperature of the internal mixer is increased to 150 ℃ and the rubber is discharged.
Two-stage mixing: mixing on a master batch roller uniformly, adding sulfur and an accelerator, cutting for 3 times, manually and alternately rolling and wrapping with a triangle bag for 5 times, discharging tablets, and cooling to room temperature.
Example 2 after 24 hours at room temperature, the test was performed.
TABLE 6 mixing hold times for examples 1, 2 series
| Examples 2 to 0 | Examples 2 to 30 | Examples 2 to 60 | Examples 2 to 90 | Examples 2 to 120 | |
| Mixing hold time/sec | 0 | 30 | 60 | 90 | 120 |
The rubber composition obtained by mixing was vulcanized in a mould prepared in advance, the vulcanization conditions being 160 ℃ for 15min and the pressure being 15 MPa. The properties of the vulcanized rubber were then measured by the following test methods, and the measurement results are shown in Table 7.
Test method for evaluating rubber properties
Physical properties:
the hardness at room temperature was measured based on GB/T531.1-2008, and the results are shown in Table 7, the higher the value, the higher the hardness.
The tensile strength measured based on GB/T528-2009 is shown as "tensile strength". In addition, the elongation at break during the same test is shown as "elongation at break". The product of tensile strength and elongation at break is shown as the "tensile product" as shown in table 7. The larger the value, the higher the reinforcing property, and the better the physical properties. The aging condition of the physical properties after aging is 100 ℃ for 48 hours, the ratio of the tensile product after aging to the tensile product before aging is the thermal aging retention rate, and the larger the value is, the better the aging resistance is.
Heat buildup:
rebound values determined based on GB/T1681-2009 are shown as "rebound", with the results shown in Table 7. The larger the value, the lower the heat generation, the more excellent the heat generation property, and the lower the rolling resistance of the resulting tire.
Dynamic performance-dynamic thermo-mechanical analysis (Dynamic thermomechanical analysis, DMA):
measured using a dynamic thermo-mechanical analyzer of the VR-7120 type manufactured by UESHIMA corporation, japan. The test conditions were: a stretch mode; frequency, 12Hz; strain, 7% ± 2%; temperature rise is 2 ℃/min. As a result, as shown in Table 7, the tan delta value at 60℃characterizes the hysteresis loss of the vulcanized rubber, and the smaller the value, the lower the hysteresis loss of the vulcanized rubber, the lower the heat generation, the more excellent the heat generation property, and the lower the rolling resistance of the resulting tire.
TABLE 7 example 2 series of test results
As can be seen from a comparison of the series of data from example 21, the longer the mixing time, the better the physical properties of the compound, the better the heat build up, which is manifested by an increase in the tensile product number, an increase in the rebound value, and a decrease in tan delta @60 ℃.
Industrial applicability
According to the invention, on the premise of not changing the components of the formula and not increasing the cost of the formula, various performances of the formula can be improved to a certain extent by optimizing the process.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art. The generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A mixing method for improving the dispersion effect of filler in rubber composition is characterized in that the filler and processing aid are firstly put into an internal mixer in the mixing stage of the method, the filler and the processing aid are stirred by rotating a rotor, the rotor speed of the internal mixer is controlled to be 40-60rpm, and the mixing is carried out by adding the rubber component after 30-200s of stirring.
2. The method of kneading for improving the dispersion of filler in a rubber composition according to claim 1, wherein the rubber component comprises one or more of isoprene rubber, polybutadiene rubber (BR), styrene-butadiene rubber (SBR), styrene-isoprene-butadiene rubber (SIBR), ethylene-propylene-diene monomer rubber (EPDM), chloroprene Rubber (CR) and nitrile rubber (NBR).
3. The method of kneading for improving the dispersion of a filler in a rubber composition according to claim 1, wherein the filler comprises one or both of carbon black and white carbon black; preferably, the BET specific surface area of the carbon black particles is 20 to 160m 2 Preferably from 40 to 130m 2 Preferably 50 to 120m 2 /g; the average secondary particle diameter of the carbon black particles is preferably 0.05 to 3. Mu.m, more preferably 0.1 to 1.0. Mu.m, still more preferably 0.2 to 0.9. Mu.m; most preferably, the carbon black is one or more of N134, N220, N234, N330, N375, N550; preferably, the BET specific surface area of the white carbon black is 50 to 250m 2 Preferably 80 to 210m per gram 2 Preferably 100 to 190m 2 /g; the average secondary particle diameter of the white carbon black is preferably 0.04 to 3. Mu.m, more preferably 0.1 to 1. Mu.m, and still more preferably 0.2 to 0.7. Mu.m.
4. The method of kneading for improving the dispersion of filler in a rubber composition according to claim 1, wherein the processing aid comprises one or two of a silane coupling agent, a dispersion resin, a rubber processing oil, an activator and an anti-aging agent.
5. The method for kneading for improving the dispersion effect of filler in a rubber composition according to claim 1, wherein the rubber composition comprises 100 parts by weight of the rubber component, which is prepared by kneading:
100 parts of rubber component
70-120 parts of white carbon black
0-20 parts of carbon black
Silane coupling agent 5.0-10.0 parts
8.0-15.0 parts of rubber operating oil;
and proper amount of activator, anti-aging agent, sulfur and promoter.
6. The method of kneading for improving the dispersion of a filler in a rubber composition according to claim 5, wherein the rubber component is 65 to 80 parts of solution polymerized styrene-butadiene rubber and 20 to 35 parts of cis-butadiene rubber.
7. A mixing method for improving the dispersion of filler in a rubber composition according to claim 5 or 6, comprising the steps of:
1. the upper auxiliary machine process comprises the following steps:
(1) controlling the rotor speed of the internal mixer to be 40-60rpm and the upper ram pressure to be 50-60N/cm 2 Adding all raw materials except rubber, including white carbon black, a silane coupling agent, rubber operating oil and other chemical auxiliary agents, lowering a top bolt, and keeping the preset time for 50-200s, wherein the temperature of cooling water of an internal mixer is 30-40 ℃;
(2) lifting the top bolt and adding rubber;
(3) lowering the top bolt to raise the temperature of the rubber material to 80-120 ℃;
(4) lifting the top bolt and keeping for 4-8s;
(5) lowering the top bolt to raise the temperature of the rubber material to 140-150 ℃, keeping the temperature of the rubber material constant at 145+/-2 ℃ by controlling the rotating speed, and mixing for 100-130s;
(6) discharging the sizing material to a lower auxiliary machine;
2. the process of the auxiliary machine comprises the following steps:
(1) heating the sizing material to 140-150 ℃;
(2) mixing at 145+/-2 ℃ for 250-400s;
(3) discharging glue to an open mill: turning over the cooled sizing material to 90-100 ℃, adding sulfur and an accelerator on an open mill for uniform dispersion, and cooling the lower piece to room temperature.
8. The method for kneading for improving the dispersion effect of filler in a rubber composition according to claim 1, wherein the rubber composition comprises 100 parts by weight of the rubber component, which is prepared by kneading:
100 parts of rubber component
40-60 parts of carbon black
2.0 to 5.0 parts of dispersion resin
3.0-10.0 parts of rubber operating oil;
and proper amount of activator, anti-aging agent, sulfur and promoter.
9. The method for kneading for improving the dispersion effect of filler in a rubber composition according to claim 1, wherein the rubber component is 30 to 50 parts of natural rubber; 50-70 parts of cis butadiene rubber.
10. A mixing process for improving the dispersion of fillers in rubber compositions according to claim 7 or 8, characterized in that the mixing of the compound of the process is carried out in two stages, one of which is carried out in a shear mixer; the two sections are mixed on a double-roller open mill, and the specific mixing process of each section is as follows:
and (3) mixing: the rotating speed of the rotor is 40-60rpm per minute; adding all raw materials except rubber, including carbon black, rubber operating oil and other chemical additives, lowering a top bolt, and keeping the preset time for 50-200s; adding rubber into the upper ram, lowering the upper ram, raising the temperature of the internal mixer to 120-140 ℃, lifting the upper ram once, and cleaning;
raising the temperature of the internal mixer to 140-160 ℃ and discharging glue;
two-stage mixing: uniformly mixing on a master batch roller, adding a sulfur and an accelerator, and cutting for 3-4 times respectively; and (5) manually and alternately rolling and wrapping the sheet by a triangular bag for 4-6 times, and cooling to room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311234293.5A CN117565258A (en) | 2023-09-22 | 2023-09-22 | Mixing method for improving filler dispersion effect in rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311234293.5A CN117565258A (en) | 2023-09-22 | 2023-09-22 | Mixing method for improving filler dispersion effect in rubber composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117565258A true CN117565258A (en) | 2024-02-20 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202311234293.5A Pending CN117565258A (en) | 2023-09-22 | 2023-09-22 | Mixing method for improving filler dispersion effect in rubber composition |
Country Status (1)
| Country | Link |
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| CN (1) | CN117565258A (en) |
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2023
- 2023-09-22 CN CN202311234293.5A patent/CN117565258A/en active Pending
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