CN117986707A - Rubber composition, preparation method thereof and bead part rubber of aviation tire - Google Patents
Rubber composition, preparation method thereof and bead part rubber of aviation tire Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 135
- 239000005060 rubber Substances 0.000 title claims abstract description 135
- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011324 bead Substances 0.000 title claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 25
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 24
- 239000006229 carbon black Substances 0.000 claims abstract description 24
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 24
- 229920003049 isoprene rubber Polymers 0.000 claims abstract description 22
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 18
- 239000011787 zinc oxide Substances 0.000 claims abstract description 13
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 11
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 claims abstract description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008117 stearic acid Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims description 28
- 238000007599 discharging Methods 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 239000003292 glue Substances 0.000 claims description 9
- 230000009477 glass transition Effects 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
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- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000945 filler Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 6
- 239000004014 plasticizer Substances 0.000 abstract description 4
- 150000003384 small molecules Chemical class 0.000 abstract description 3
- 239000004636 vulcanized rubber Substances 0.000 abstract description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 23
- 238000003825 pressing Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 14
- 230000020169 heat generation Effects 0.000 description 11
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 6
- 239000013543 active substance Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000010692 aromatic oil Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 101100478969 Oryza sativa subsp. japonica SUS2 gene Proteins 0.000 description 2
- 101100004663 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) BRR2 gene Proteins 0.000 description 2
- 101100504519 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) GLE1 gene Proteins 0.000 description 2
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- 241001441571 Hiodontidae Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- 229920002521 macromolecule Polymers 0.000 description 1
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- 229920001206 natural gum Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000417 polynaphthalene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application provides a rubber composition, which comprises the following components in parts by weight: 50-85 parts of isoprene rubber, 10-30 parts of butadiene rubber, 2-10 parts of high styrene rubber, 5-10 parts of trans-isooctene rubber, 3-10 parts of zinc oxide, 0.5-5 parts of stearic acid, 0.5-2 parts of hydroquinone anti-aging agent, 0.5-2 parts of ketoamine anti-aging agent, 50-80 parts of reinforcing agent, 0.1-0.5 part of scorch retarder, 1.0-3.0 parts of accelerator and 2-5 parts of vulcanizing agent. The application provides a preparation method and application of a rubber composition. According to the rubber composition provided by the application, the trans-isooctene rubber is used for replacing plasticizers such as aromatic hydrocarbon oil, so that the processability is improved, the content of small molecule mobile substances is reduced, and the high styrene rubber is added, so that the carbon black consumption is reduced, and the modulus of vulcanized rubber is improved.
Description
Technical Field
The invention relates to the technical field of rubber, in particular to a rubber composition, a preparation method thereof and a bead part rubber of an aviation tire.
Background
With the continuous progress of technology, the aircraft tire is also advanced from the original heavy bias structure to the lighter meridian structure, so that the fuel consumption of the aircraft is greatly reduced, and the requirements on the structural design and the formula design of the tire are also improved. The radial tire has a low level relative to the bias structure, and the bead part rubber is used as a contact part between the tire and the rim, so that the radial tire is required to have a high modulus and good rebound performance to ensure the air tightness of the tire, and has low heat generation, good wear resistance and good fatigue resistance. When the aircraft tire runs, the bead part and the rim repeatedly rub to generate heat, so that small molecular substances in the part glue are easily promoted to migrate out, and a color reaction occurs under the condition of illumination.
In order to improve the adhesion performance with the inner liner, a large amount of tackifying resin such as C5 petroleum resin and phenolic tackifying resin is added into the conventional aviation tire bead site glue, a large amount of carbon black is filled into the bead site glue in order to improve the modulus of the bead site glue, and an oil plasticizer is added in order to improve the processability. The tackifying resin or the oil contains a large amount of chromophores, the chromophores migrate to the surface to display different colors under the high temperature conditions such as summer and the like, the color is changed after the bead rubber strip is formed and is parked for a short time, and the appearance and the subsequent green tyre forming are affected. On the other hand, the bead part glue of the aviation tire is positioned at the tire bead part and is contacted with the rim, so the bead part glue is required to have higher modulus, the modulus is often improved in the industry by improving the filling amount of carbon black, adding reinforcing resin into the formula and the like, and the heat generation of the bead part glue is greatly improved by adding reinforcing resin or reinforcing agent.
The existing problems of color development and color development of the sizing material are mainly solved by adding a polyol substance, a special active agent and a mixture of polynaphthalene and adopting a principle of sealing and controlling small molecules by macromolecules to reduce the migration of the small molecules, however, the original substances such as a plasticizer, a dispersing agent and the like are needed to be removed when the substances are actually used, so that other performances of the sizing material are reduced. Another solution is to soak or brush the shaped article with the anti-blooming agent, which can only avoid the phenomena of blooming, bluing and flooding in a short time. Therefore, neither of the above methods can fundamentally solve the problem of flooding, and achieve high modulus, low heat generation, and good abrasion resistance while simultaneously achieving the same.
Disclosure of Invention
The technical problem solved by the invention is to provide the rubber composition which has high modulus, low heat generation, good wear resistance and difficult color development.
In view of this, the present application provides a rubber composition comprising, in parts by weight: 50-85 parts of isoprene rubber, 10-30 parts of butadiene rubber, 2-10 parts of high styrene rubber, 5-10 parts of trans-isooctene rubber, 3-10 parts of zinc oxide, 0.5-5 parts of stearic acid, 0.5-2 parts of hydroquinone anti-aging agent, 0.5-2 parts of ketoamine anti-aging agent, 50-80 parts of reinforcing agent, 0.1-0.5 part of scorch retarder, 1.0-3.0 parts of accelerator and 2-5 parts of vulcanizing agent.
Preferably, the cis-1, 4-structure content of the isoprene rubber is more than 97%, the Mooney viscosity ML (1+4) is 75-85 at 100 ℃, the ash content is less than or equal to 0.5%, and the volatile component is less than or equal to 0.7%.
Preferably, the butadiene rubber is butadiene rubber with the cis-1, 4-structure content of 95-98 percent.
Preferably, the high styrene rubber has a bound styrene content of 65% to 70%.
Preferably, the Mooney viscosity ML (1+4) of the trans-isooctane rubber is less than 10, the glass transition temperature is-60 to-70 ℃, and the melting point is 50 to 60 ℃.
Preferably, the reinforcing agent is selected from one or more of N234 carbon black, N330 carbon black, N339 carbon black and N351 carbon black, the sulfur comprises oil-extended insoluble sulfur, the oil content of the oil-extended insoluble sulfur is 19-21%, and the insoluble sulfur content is more than or equal to 90%.
Preferably, the trans-isooctene rubber is VN8012, and the content of the trans-isooctene rubber is 6-8 parts.
The application also provides a preparation method of the rubber composition, which comprises the following steps:
According to the weight parts, isoprene rubber, butadiene rubber, high styrene rubber, trans-isooctene rubber, zinc oxide, stearic acid, hydroquinone anti-aging agent and ketoamine anti-aging agent are subjected to one-stage mixing to obtain a one-stage mixed rubber sheet;
And (3) carrying out two-stage mixing on the first-stage mixing film, the scorch retarder, the accelerator and the vulcanizing agent to obtain the rubber composition.
Preferably, the feeding temperature of the first-stage mixing is 50-80 ℃, the filling coefficient is 60-70%, and the glue discharging temperature is 150-170 ℃; the feeding temperature of the two-stage mixing is 50-80 ℃, and the rubber discharging temperature is 100-110 ℃.
The application also provides a bead part rubber of the aviation tire, which comprises a rubber composition, wherein the rubber composition is prepared by the rubber composition or the preparation method.
The application provides a rubber composition, which comprises specific content of isoprene rubber, butadiene rubber, high styrene rubber, trans-isooctene rubber, zinc oxide, stearic acid, hydroquinone anti-aging agent, ketoamine anti-aging agent, reinforcing agent, scorch retarder, accelerator and vulcanizing agent; in the rubber composition, through introducing isoprene rubber, the adhesiveness of the mixed rubber is good, the adhesiveness of the rubber end part of the seam allowance part and the rubber of the airtight layer part is improved, trans-isooctene rubber is used for replacing aromatic oil, the processability of the mixed rubber is improved, the concentration of a chromogenic group is reduced, the color problem is avoided, the introduction of high-styrene rubber and the reduction of a reinforcing agent are avoided, and the modulus and flexibility of the rubber composition are improved; therefore, the rubber composition provided by the application has the advantages of high modulus, flexibility, low heat generation, good wear resistance and difficult color development.
Drawings
FIG. 1 is a photograph of a semi-finished rubber strip prepared in examples and comparative examples of the present invention after being placed.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
In view of the performance requirements of the bead site rubber of the aircraft tire in the prior art, the application provides a rubber composition, which has the advantages of low heat generation, good wear resistance and difficult color development when being applied to the bead site rubber by introducing isoprene rubber, butadiene rubber, high styrene rubber, trans-isooctene rubber, an active agent, an anti-aging agent, a reinforcing agent, a scorch retarder, an accelerator and a vulcanizing agent. Specifically, the embodiment of the application discloses a rubber composition, which comprises the following components in parts by weight: 50-85 parts of isoprene rubber, 10-30 parts of butadiene rubber, 2-10 parts of high styrene rubber, 5-10 parts of trans-isooctene rubber, 3-10 parts of zinc oxide, 0.5-5 parts of stearic acid, 0.5-2 parts of hydroquinone anti-aging agent, 0.5-2 parts of ketoamine anti-aging agent, 50-80 parts of reinforcing agent, 0.1-0.5 part of scorch retarder, 1.0-3.0 parts of accelerator and 2-5 parts of vulcanizing agent.
In the rubber composition, the isoprene rubber is used as a main rubber, raw rubber does not need to be plasticated before mixing, the adhesiveness can be ensured, and the adhesiveness with the inner liner rubber is improved. The cis-1, 4-structure content of the isoprene rubber is more than 97%, the Mooney viscosity ML (1+4) is 75-85 ℃ at 100 ℃, the ash content is less than or equal to 0.5%, and the volatile component is less than or equal to 0.7%; wherein, the higher the cis-1, 4-structure content is, the better the tensile property is, the higher the ash content and the volatile content is, the worse the sizing property is, and the Mooney viscosity is controlled, the better the processing stability is. The content of the isoprene rubber is 50 to 85 parts by weight, specifically, the content of the isoprene rubber is 53 to 83 parts by weight, more specifically, the content of the isoprene rubber is 55 parts by weight, 58 parts by weight, 62 parts by weight, 65 parts by weight, 69 parts by weight, 71 parts by weight, 74 parts by weight, 76 parts by weight, 78 parts by weight, 80 parts by weight, 81 parts by weight, 82 parts by weight, or 83 parts by weight.
The cis-butadiene rubber has an influence on the modulus of the rubber composition, and is cis-butadiene rubber with the cis-1, 4-structure content of 95-98%, and the cis-butadiene rubber with the high cis-structure content is beneficial to improving the flex fatigue resistance and the wear resistance of the rubber material. The content of the butadiene rubber is 10 to 30 parts by weight, specifically, the content of the butadiene rubber is 12 to 28 parts by weight, more specifically, the content of the butadiene rubber is 15 parts by weight, 17 parts by weight, 20 parts by weight, 21 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight or 28 parts by weight.
The high styrene rubber is beneficial to improving the modulus of the rubber composition and reducing the heat generating property, and the content of the combined styrene is 65-70%. The content of the high styrene rubber is 2-10 parts by weight, specifically, the content of the high styrene rubber is 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight.
The trans-isooctene rubber replaces aromatic oil, improves the processability of mixed rubber, reduces the concentration of chromogenic groups, and can effectively avoid the problem of color flooding after long-time use. The Mooney viscosity ML (1+4) of the trans-isooctene rubber is less than 10, the glass transition temperature is-60 to-70 ℃, and the melting point is 50-60 ℃; the trans-isooctene rubber has low glass transition temperature, which is favorable for the low-temperature service performance of the rubber, and low Mooney viscosity, which is favorable for improving the processing plasticity of the rubber material, and the proper melting point ensures that the rubber material has good stiffness at low temperature and does not influence the processing performance at high temperature. In the present application, the trans-isooctene rubber is VN8012 provided by Yingchang Desoxite chemical company. The content of the trans-isooctene rubber is 5-10 parts by weight, specifically, the content of the trans-isooctene rubber is 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight.
The zinc oxide and the stearic acid are used as active agents, and interact to generate zinc soap, so that the solubility of the zinc oxide in rubber is improved, and the zinc oxide and the accelerator are reacted to form a complex with good solubility in the rubber, so that the accelerator and the vulcanizing agent are activated, and the vulcanizing effect is improved. The content of the zinc oxide is 3-10 parts by weight, specifically, the content of the zinc oxide is 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight. The content of the stearic acid is 0.5-5 parts by weight, specifically, the content of the stearic acid is 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight.
The hydroquinone anti-aging agent is mainly used for protecting flexural fatigue, and the ketoamine anti-aging agent is mainly used for protecting thermo-oxidative aging; the content of the hydroquinone anti-aging agent is 0.5-2 parts by weight, specifically, the content of the ketoamine anti-aging agent is 0.5 parts by weight, 0.7 parts by weight, 0.9 parts by weight, 1.0 parts by weight, 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, 1.9 parts by weight or 2.0 parts by weight, and specifically, the content of the ketoamine anti-aging agent is 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, 1.0 parts by weight, 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight or 2.0 parts by weight.
The reinforcing agent is used for improving the high wear resistance of the rubber composition, is specifically selected from high wear resistance carbon black, and more specifically, is selected from one or more of N234 carbon black, N330 carbon black, N339 carbon black and N351 carbon black; the content of the reinforcing agent is 50 to 80 parts by weight, specifically 52 to 65 parts by weight, more specifically 53 parts by weight, 54 parts by weight, 55 parts by weight, 56 parts by weight, 57 parts by weight, 58 parts by weight, 59 parts by weight, 60 parts by weight, 61 parts by weight, 62 parts by weight, 63 parts by weight, 64 parts by weight or 65 parts by weight.
The content of the scorch retarder is 0.1 to 0.5 weight part, specifically, the content of the scorch retarder is 0.1 weight part, 0.2 weight part, 0.3 weight part, 0.4 weight part or 0.5 weight part. In a specific embodiment, the scorch retarder is specifically a scorch retarder CTP-80.
The accelerator is specifically a sulfenamide accelerator, the content of which is 1.0-3.0 parts by weight, specifically the content of the accelerator is 1.2-2.7 parts by weight, more specifically 1.3 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, 1.9 parts by weight, 2.0 parts by weight, 2.1 parts by weight, 2.2 parts by weight, 2.3 parts by weight, 2.4 parts by weight, 2.5 parts by weight, 2.6 parts by weight or 2.7 parts by weight.
The vulcanizing agent is specifically insoluble sulfur, more specifically oil-filled insoluble sulfur, the oil content of the vulcanizing agent is 19-21%, and the insoluble sulfur content is more than or equal to 90%. The content of the vulcanizing agent is 2 to 5 parts by weight, specifically, the content of the vulcanizing agent is 2.5 to 4.5 parts by weight, and more specifically, the content of the vulcanizing agent is 3 to 4 parts by weight.
The application also provides a preparation method of the rubber composition, which comprises the following steps:
According to the weight parts, isoprene rubber, butadiene rubber, high styrene rubber, trans-isooctene rubber, zinc oxide, stearic acid, hydroquinone anti-aging agent and ketoamine anti-aging agent are subjected to one-stage mixing to obtain a one-stage mixed rubber sheet;
And (3) carrying out two-stage mixing on the first-stage mixing film, the scorch retarder, the accelerator and the vulcanizing agent to obtain the rubber composition.
In the preparation process of the rubber composition, the preparation method of the one-stage mixed rubber sheet specifically comprises the following steps:
One-stage mixing is carried out in an internal mixer, the filling coefficient is kept between 65% and 70%, the rotating speed is 30-50 rpm, the feeding temperature is 50-80 ℃, raw isoprene rubber, butadiene rubber, high styrene rubber and trans-isooctene rubber are added, a top bolt is pressed for 80-100 s, an active agent and an anti-aging agent are added into the top bolt, the top bolt is pressed for 50-60 s, a bolt is lifted, 1/2 carbon black reinforcing agent is added, the top bolt is pressed for 20-40 s, the bolt is lifted, the rest 1/2 carbon black reinforcing agent is added, the bolt is lifted after 10-30 s, the time is kept for 5-20 s, the bolt is again pressed for 10-30 s, the bolt is lifted and kept for 5-20 s, the bolt is pressed, the rubber is discharged at 150-170 ℃, the open mill is placed at room temperature for at least 8h.
The two-stage mixing step specifically comprises the following steps:
Mixing in an internal mixer at 10-30 rpm, feeding at 50-80 deg.c, adding one section of mixing film, antiscorching agent, promoter and vulcanizing agent, pressing for 100-130 s, raising the bolt for 8-12 s, pressing the bolt again, discharging at 100-110 deg.c, feeding in an open mill, and standing at room temperature.
The application also provides a bead part rubber of the aviation tire, which comprises a rubber composition, wherein the rubber composition is the rubber composition in the scheme.
In order to further understand the present invention, the rubber composition, the preparation method and the application thereof provided by the present invention are described in detail with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Examples 1 to 3
And (3) mixing: mixing in an internal mixer, keeping the filling coefficient between 65% and 70%, rotating at 40rpm, feeding at 60 ℃, adding raw isoprene rubber, butadiene rubber, high styrene rubber and trans-isooctene rubber, pressing a top bolt for 90s, adding an active agent and an anti-aging agent into the top bolt, pressing the top bolt for 60s, lifting the top bolt, adding 1/2 carbon black reinforcing agent, pressing the top bolt for 30s, lifting the top bolt, adding the rest 1/2 carbon black reinforcing agent, lifting the top bolt for 20s, keeping for 10s, pressing the top bolt for 20s again, lifting the top bolt for 10s, pressing the top bolt, discharging rubber at 160 ℃, opening the mixer, and standing at room temperature for at least 8h;
Two-stage mixing: mixing in an internal mixer at 20rpm, feeding at 70deg.C, adding a section of mixing film, scorch retarder, accelerator and vulcanizing agent, pressing for 120s, lifting the bolt for 10s, pressing the bolt again, discharging rubber at 105deg.C, discharging the rubber sheet in an open mill, and standing at room temperature to obtain rubber samples, wherein the contents of the components are shown in Table 1.
Comparative examples 1 to 8
The natural rubber RSS1# is plasticated by an open mill before being mixed, so that the temperature of a door ML (1+4) is reduced to 50-70 ℃ and is used after being parked for at least 4 hours;
And (3) mixing: mixing in an internal mixer, keeping the filling coefficient between 65% and 70%, keeping the rotation speed at 40rpm, adding plasticated natural rubber RSS1#, isoprene rubber, butadiene rubber, high styrene rubber and trans-isooctene rubber at 60 ℃, pressing a top bolt for 90s, adding an active agent and an anti-aging agent into the top bolt, pressing the top bolt for 60s, lifting the bolt, adding 1/2 carbon black reinforcing agent, pressing the top bolt for 30s, lifting the bolt, adding the rest 1/2 carbon black reinforcing agent and aromatic oil, lifting the bolt after 20s, keeping for 10s, pressing the bolt for 20s again, lifting the bolt for 10s, pressing the bolt, discharging rubber at 160 ℃, opening the mixer, and standing at room temperature for at least 8h;
Two-stage mixing: mixing in an internal mixer at 20rpm, feeding at 70deg.C, adding a section of mixing film, tackifying resin SL-1801, scorch retarder, accelerator, vulcanizing agent, pressing for 120s, lifting and holding for 10s, pressing again, discharging at 105deg.C, discharging, and standing at room temperature to obtain rubber sample, wherein the contents of the above components are shown in Table 1.
The rubber samples prepared in examples and comparative examples were subjected to performance tests, the mix and vulcanizate test conditions were as follows, and the test results are shown in Table 2:
1) T5@120℃Mooney scorch time test: testing was performed at 120 ℃ using a mooney viscometer according to GB/T1232.4 standard;
2) ML (1+4) 100 ℃ test: the Mooney viscosity test is carried out according to the GB/T1232.1 standard;
3) Tensile property test: the method comprises the steps of performing tensile test on a sample by using a Z005 type Zwick tensile machine optical extensometer according to GB/T528-2009 standard, wherein a test spline is an I-type spline, the gauge length is 25mm, and the tensile speed is 500mm/min;
4) Hardness testing: samples with a thickness > 6mm were tested using Shore A hardness;
5) Heat generation test: according to GB/T1687.3-2016, the test is carried out under the conditions that the temperature of a thermostatic chamber is 55 ℃, the stroke is 5.71mm and the prestress is 1.0 MPa;
6) DIN abrasion loss: test condition setting the test process of the sample selects a rotary sample, loads 50N, travels 20m, and calculates the loss mass before and after the test.
Table 1 Table of the formulation data (parts by weight) for the examples and comparative examples rubber samples
Table 2 table of physical properties of compounds and vulcanizates prepared in examples and comparative examples
Comparative example 1 is a conventional natural gum formulation, comparative example 2 is a plasticizer-free gum formulation, and comparative example 3 is a conventional gum formulation.
As can be seen from the physical property test table in Table 2, in comparative example 2, the Mooney viscosity was improved to be reduced in processability, the carbon black loading was greatly reduced, the Mooney viscosity was improved to be improved in processability, the heat generation was greatly reduced, the compression set was in the range of (4.9 to 6.6)%, and the tensile properties, the abrasion resistance and the yield resistance were all maintained at the levels equivalent to those of comparative examples, as compared with comparative examples 1 to 3, after the plasticizer was removed.
Comparative example 4 compared with example 1, the substitution of isoprene rubber for butadiene rubber reduced the processability of the compound rubber, increased DIN abrasion of the vulcanized rubber and deteriorated flexibility; comparative example 5 compared with example 1, butadiene rubber was replaced with 10 parts of high styrene rubber and 10 parts of trans-isooctene rubber, the heat generation temperature of the vulcanized rubber was increased, DIN abrasion was increased, and flexibility was deteriorated; comparative example 6 compared with example 1, the high styrene rubber was replaced with the trans-isooctene rubber, the rubber modulus was too low and the hardness was too low, and comparative example 7 compared with example 3, when the high styrene rubber was removed from the formulation, the rubber modulus was too low, the elongation was decreased when the cis-butadiene content was high, and when the VN8012 usage was too large, the elongation was decreased significantly; in comparative example 8, in the case where isoprene rubber was used instead of VN8012, butadiene rubber was used, but the amount of the carbon black to be kneaded was too large, the kneading was not uniform, and the flex fatigue resistance was poor.
Therefore, in combination with the above effects of elongation at break, hardness, elongation, heat generation, DIN abrasion, flexural performance, the rubber properties of the examples of the present application are superior to those of the comparative examples, and the heat generation of comparative examples 1 to 3 is excessively high, the flexural fatigue resistance of comparative examples 4 and 5 is poor, the modulus of comparative examples 6 and 7 is excessively low, and the flexural fatigue resistance of comparative example 8 is poor.
FIG. 1 shows the extruded semi-finished product sample bars of the examples and the comparative examples, which are placed under the sunlight at the temperature of (38+/-2) ℃ for 7 days, and the surface of the sample bars is in a surface loading state after the sample bars are placed for 7 days, as shown in FIG. 1, the surface of the sample bars is obviously sprayed with blue and color, and the sample bars of the comparative example 2 are not discolored in a state of being filled with oil. Examples 1 to 3 showed no discoloration of the surface of the gel strip.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
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, and 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 rubber composition comprises the following components in parts by weight: 50-85 parts of isoprene rubber, 10-30 parts of butadiene rubber, 2-10 parts of high styrene rubber, 5-10 parts of trans-isooctene rubber, 3-10 parts of zinc oxide, 0.5-5 parts of stearic acid, 0.5-2 parts of hydroquinone anti-aging agent, 0.5-2 parts of ketoamine anti-aging agent, 50-80 parts of reinforcing agent, 0.1-0.5 part of scorch retarder, 1.0-3.0 parts of accelerator and 2-5 parts of vulcanizing agent.
2. The rubber composition according to claim 1, wherein the isoprene rubber has a cis-1, 4-structure content of > 97%, a Mooney viscosity ML (1+4) at 100℃of 75 to 85, an ash content of 0.5% or less and a volatile content of 0.7% or less.
3. The rubber composition according to claim 1, wherein the butadiene rubber is a cis-1, 4-structure content of 95 to 98%.
4. The rubber composition according to claim 1, wherein the high styrene rubber has a bound styrene content of 65% to 70%.
5. The rubber composition according to claim 1, wherein the trans-isooctane rubber has a Mooney viscosity ML (1+4) at 100 ℃ below 10, a glass transition temperature of-60 to-70 ℃ and a melting point of 50 to 60 ℃.
6. The rubber composition according to claim 1, wherein the reinforcing agent is one or more selected from the group consisting of N234 carbon black, N330 carbon black, N339 carbon black and N351 carbon black, the sulfur comprises oil-extended insoluble sulfur having an oil content of 19 to 21% and an insoluble sulfur content of 90% or more.
7. The rubber composition according to claim 1, wherein the trans-isooctene rubber is VN8012 and the content thereof is 6 to 8 parts.
8. The method for producing a rubber composition as claimed in claim 1, comprising the steps of:
According to the weight parts, isoprene rubber, butadiene rubber, high styrene rubber, trans-isooctene rubber, zinc oxide, stearic acid, hydroquinone anti-aging agent and ketoamine anti-aging agent are subjected to one-stage mixing to obtain a one-stage mixed rubber sheet;
And (3) carrying out two-stage mixing on the first-stage mixing film, the scorch retarder, the accelerator and the vulcanizing agent to obtain the rubber composition.
9. The preparation method according to claim 8, wherein the feeding temperature of the one-stage mixing is 50-80 ℃, the filling coefficient is 60-70%, and the glue discharging temperature is 150-170 ℃; the feeding temperature of the two-stage mixing is 50-80 ℃, and the rubber discharging temperature is 100-110 ℃.
10. A bead filler for an aircraft tire, comprising a rubber composition, which is the rubber composition according to any one of claims 1 to 7 or the rubber composition produced by the production method according to any one of claims 8 to 9.
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