CN114213722A - Run-flat tire support rubber composition, preparation and application thereof - Google Patents
Run-flat tire support rubber composition, preparation and application thereof Download PDFInfo
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- CN114213722A CN114213722A CN202111461435.2A CN202111461435A CN114213722A CN 114213722 A CN114213722 A CN 114213722A CN 202111461435 A CN202111461435 A CN 202111461435A CN 114213722 A CN114213722 A CN 114213722A
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- 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
Abstract
The invention relates to the technical field of semi-steel run-flat radial tire rubber materials, in particular to run-flat tire support rubber and a preparation method thereof. Preparing a supporting rubber for a run-flat tire by mixing cis-1, 4-polyisoprene rubber, cis-1, 4-polybutadiene rubber, carbon black, an air inhibitor and methyl resin; a new cross-linked network of the supporting adhesive is added through the methyl resin A250, so that the hardness and the modulus of the adhesive are obviously improved; the carbon black is partially replaced by the air inhibitor with small heat generation, so that the heat generation is reduced; the support rubber is used for a run-flat tire, and heat generation is reduced.
Description
Technical Field
The invention relates to the technical field of semi-steel run-flat radial tire rubber materials, in particular to a run-flat tire supporting rubber composition, and preparation and application thereof.
Background
At present, a carbon black reinforcing system and an anti-reversion agent are generally adopted in a formula of a semi-steel run-flat support adhesive to improve the modulus of the adhesive, and although the performance requirements can be met, the requirements on the modulus, the hardness and the heat generation of the support adhesive are very high because the use conditions of the support adhesive are harsh; when the two materials are used, the consumption of carbon black is large, and the rubber material has high heat generation, so that the performance of the finished tire is influenced.
Therefore, there is a need for a run-flat tire support compound that has low heat generation while maintaining hardness.
Disclosure of Invention
The invention aims to provide a run-flat tire support rubber composition, and preparation and application thereof.
The technical scheme for realizing the purpose is as follows:
the run-flat tire support rubber composition is prepared by mixing the following raw materials in parts by weight: 1-60 parts of cis-1, 4-polyisoprene rubber, 1-80 parts of cis-1, 4-polybutadiene rubber, 50-120 parts of carbon black, 1-50 parts of air inhibitor and 1-30 parts of methyl methacrylate resin.
Preferably, the cis content of the cis-1, 4-polyisoprene rubber is more than 97%.
Preferably, the cis content of the cis-1, 4-polybutadiene rubber is more than 95%.
Preferably, the nitrogen adsorption specific surface area of the carbon black is 70m2More than g and DBP oil absorption value of 80cm3More than 100 g.
Preferably, the air blocking agent employs NM 360.
Preferably, the methyl resin adopts a bonding resin A250.
Preferably, the vulcanization accelerator also comprises an accelerator, sulfur and an anti-reversion agent; the accelerator is N-tertiary butyl-2-benzothiazole sulfonamide or N, N-2 dicyclohexyl-2, 2-dibenzothiazyl sulfenamide, and the dosage range is 0.1-5 parts; the sulfur is insoluble sulfur HD OT 20, and the dosage range is 2-10 parts; the vulcanization reversion agent is WY9188, and the dosage range is 0.1-5 parts.
A preparation method of run-flat tire support rubber comprises the following steps:
(1) non-productive mixing stage: mixing cis-1, 4-polyisoprene rubber, cis-1, 4-polybutadiene rubber, carbon black, an air inhibitor and methyl resin until the temperature reaches 140 ℃ to obtain a first mixture;
(2) a productive mixing stage: adding an accelerator, sulfur and an anti-vulcanization reversion agent into the first mixture obtained in the step (1), and mixing until the temperature reaches 115 ℃ to obtain a second mixture;
(3) and (3) a vulcanization stage: and (3) vulcanizing the second mixture obtained in the step (2) to obtain the support rubber.
Further, the number of the non-productive kneading stages is plural; the technological parameters of the plurality of non-productive mixing stages are the same; the interval time of a plurality of non-productive mixing stages is 4h-720 h; the interval time between the non-productive mixing stage and the productive mixing stage is 4-720 h.
Preferably, the rotating speed of the mixing mill is 20-60 r/min.
A run-flat tire, wherein the support rubber of the tire adopts the support rubber composition of any one of the technical schemes.
The invention has the beneficial effects that:
the invention provides a run-flat tire supporting rubber composition, a preparation method and an application thereof, wherein the supporting rubber for the run-flat tire is prepared by mixing cis-1, 4-polyisoprene rubber, cis-1, 4-polybutadiene rubber, carbon black, an air inhibitor and methyl resin; a new cross-linking network of the supporting adhesive is added through the methyl resin A250, so that the hardness and modulus of the adhesive are obviously improved, and the heat generation is reduced; the carbon black is partially replaced by the air inhibitor with small heat generation, so that the heat generation is reduced; the support rubber is used for a run-flat tire, and heat generation is reduced.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Description of the components of the invention:
carbon black: the nitrogen adsorption specific surface area is 70m2More than g and DBP oil absorption value of 80cm3More than 100 g.
Air inhibitor NM 360: after being extracted from high-quality low-volatile asphalt clean coal, the rubber filler is subjected to multi-level deep processing to form the green and environment-friendly rubber filler, has lower specific gravity than carbon black, and has a lamellar structure and better reinforcement effect. The carbon black reinforcing agent is applied to the formula of the support rubber for run-flat use, and has lower heat generation performance than the traditional carbon black reinforcing system.
M-methyl resin a 250: the green, high-performance and environment-friendly modified resorcinol-formaldehyde resin has extremely low content of free resorcinol, almost no volatile matter, and has the functions of hardening and reinforcing. The meta-methyl resin A250 is applied to the formula of the run-flat supporting adhesive, so that a new cross-linked network structure in the adhesive can be increased, the cross-linked density of the adhesive is improved, and the hardness and modulus of the adhesive are improved.
Example 1
The run-flat tire support rubber composition is prepared by mixing the following raw materials in parts by weight: 30 parts of cis-1, 4-polyisoprene rubber, 70 parts of cis-1, 4-polybutadiene rubber, 30 parts of carbon black, 30 parts of an air inhibitor and 5 parts of methyl methacrylate resin.
Based on the above examples, the cis content of the cis-1, 4-polyisoprene rubberAbove 97%. The cis content of the cis-1, 4-polybutadiene rubber is more than 95 percent. The nitrogen adsorption specific surface area of the carbon black is 70m2More than g and DBP oil absorption value of 80cm3More than 100 g. The air inhibitor employs NM 360. The methyl resin adopts adhesive resin A250. Also comprises 2 parts of accelerant, 4 parts of sulfur and 2 parts of anti-reversion agent.
Example 2
The run-flat tire support rubber composition is prepared by mixing the following raw materials in parts by weight: 35 parts of cis-1, 4-polyisoprene rubber, 65 parts of cis-1, 4-polybutadiene rubber, 35 parts of carbon black, 35 parts of an air inhibitor and 8 parts of methyl methacrylate resin.
Based on the above examples, the cis content of the cis-1, 4-polyisoprene rubber is 97% or more. The cis content of the cis-1, 4-polybutadiene rubber is more than 95 percent. The nitrogen adsorption specific surface area of the carbon black is 70m2More than g and DBP oil absorption value of 80cm3More than 100 g. The air inhibitor employs NM 360. The methyl resin adopts adhesive resin A250. Also comprises 2 parts of accelerant, 4 parts of sulfur and 2 parts of anti-reversion agent.
Example 3
The run-flat tire support rubber composition is prepared by mixing the following raw materials in parts by weight: 1 part of cis-1, 4-polyisoprene rubber, 1 part of cis-1, 4-polybutadiene rubber, 50 parts of carbon black, 1 part of air inhibitor and 1 part of methyl resin.
Based on the above examples, the cis content of the cis-1, 4-polyisoprene rubber is 97% or more. The cis content of the cis-1, 4-polybutadiene rubber is more than 95 percent. The nitrogen adsorption specific surface area of the carbon black is 70m2More than g and DBP oil absorption value of 80cm3More than 100 g. The air inhibitor employs NM 360. The methyl resin adopts adhesive resin A250. Also comprises 0.1 part of accelerant, 2 parts of sulfur and 0.1 part of anti-reversion agent.
Example 4
The run-flat tire support rubber composition is prepared by mixing the following raw materials in parts by weight: 60 parts of cis-1, 4-polyisoprene rubber, 80 parts of cis-1, 4-polybutadiene rubber, 120 parts of carbon black, 50 parts of an air inhibitor and 30 parts of methyl resin.
Based on the above examples, the cis content of the cis-1, 4-polyisoprene rubber is 97% or more. The cis content of the cis-1, 4-polybutadiene rubber is more than 95 percent. The nitrogen adsorption specific surface area of the carbon black is 70m2More than g and DBP oil absorption value of 80cm3More than 100 g. The air inhibitor employs NM 360. The methyl resin adopts adhesive resin A250. Also comprises 5 parts of accelerant, 10 parts of sulfur and 5 parts of anti-reversion agent.
Comparative example 1
Table 1 shows that sample a is a control, without the use of an air blocker and a methyl resin; sample b is the support gel prepared in example 1.
A support gum having the composition as specified in Table 1 was prepared in a Banbury mixer using two separate feed mixing stages, a non-productive mixing stage and a productive mixing stage. The non-productive stage is carried out for about 2-3min until the rubber temperature reaches 140 ℃, and the process is finished. A productive mixing stage, mixing until the rubber temperature reaches 115 ℃; and vulcanizing at 151 ℃ for 30min to obtain a vulcanized sample a and a vulcanized sample b. The apparent and physical properties of the cured samples a and b are given in table 2.
TABLE 1
TABLE 2
Comparative example 2
In table 3, sample c is a control sample, with no air blocker and no methyl resin; sample d is the support gel prepared in example 1.
The rubber compositions having the ingredients specified in Table 3 were prepared in a Banbury mixer using two separate feed mixing stages, a non-productive mixing stage and a productive mixing stage. And (3) respectively mixing for about 2-3min in the non-productive stage until the rubber temperature reaches 140 ℃, and finishing. A productive mixing stage, mixing until the rubber temperature reaches 115 ℃; and vulcanizing at 151 ℃ for 30min to obtain a vulcanized sample a and a vulcanized sample b. The apparent and physical properties of the cured samples c and d are given in table 4.
TABLE 3
TABLE 4
These results show that the use of the air inhibitor NM360 and the methyl resin A250 in the formulation of run-flat support gels results in a significant reduction in heat build-up and a significant increase in modulus of the gel.
Hardness, 60 ℃ tan. delta. may be carried out according to test method GB/T531.1 acceptable to the tire industry, MH, ML may be carried out according to test method GB/T16584 acceptable to the tire industry. The lower the tan delta value at 60 ℃, the lower the heat generation of the compound; the higher the hardness, MH-ML values, the higher the hardness and modulus of the compound.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. The run-flat tire support rubber composition is characterized by being prepared by mixing the following raw materials in parts by weight: 1-60 parts of cis-1, 4-polyisoprene rubber, 1-80 parts of cis-1, 4-polybutadiene rubber, 50-120 parts of carbon black, 1-50 parts of air inhibitor and 1-30 parts of methyl methacrylate resin.
2. The run-flat tire support gum composition of claim 1, wherein: the cis content of the cis-1, 4-polyisoprene rubber is more than 97 percent.
3. The run-flat tire support gum composition of claim 1, wherein: the cis content of the cis-1, 4-polybutadiene rubber is more than 95 percent.
4. The run-flat tire support gum composition of claim 1, wherein: the nitrogen adsorption specific surface area of the carbon black is 70m2More than g and DBP oil absorption value of 80cm3More than 100 g.
5. The run-flat tire support gum composition of claim 1, wherein: the air inhibitor adopts NM 360; the methyl resin adopts adhesive resin A250.
6. The run-flat tire support gum composition of claim 1, wherein: also comprises 0.1 to 5 weight portions of accelerant, 2 to 10 weight portions of sulfur and 0.1 to 5 weight portions of anti-vulcanization reversion agent.
7. A preparation method of run-flat tire support rubber is characterized by comprising the following steps:
(1) non-productive mixing stage: mixing cis-1, 4-polyisoprene rubber, cis-1, 4-polybutadiene rubber, carbon black, an air inhibitor and methyl resin until the temperature reaches 140 ℃ to obtain a first mixture;
(2) a productive mixing stage: adding an accelerator, sulfur and an anti-vulcanization reversion agent into the first mixture obtained in the step (1), and mixing until the temperature reaches 115 ℃ to obtain a second mixture;
(3) and (3) a vulcanization stage: and (3) vulcanizing the second mixture obtained in the step (2) to obtain the support rubber.
8. The method for preparing a run-flat tire support compound according to claim 7, wherein: the number of the nonproductive kneading stages is plural.
9. The method for preparing a run-flat tire support compound according to claim 7, wherein: the rotating speed of the mixing roll is 20-60 r/min.
10. A run-flat tire characterized by: the support rubber composition of any one of claims 1 to 7 is used for the support rubber of the tire.
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| CN202111461435.2A CN114213722A (en) | 2021-12-02 | 2021-12-02 | Run-flat tire support rubber composition, preparation and application thereof |
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| CN202111461435.2A CN114213722A (en) | 2021-12-02 | 2021-12-02 | Run-flat tire support rubber composition, preparation and application thereof |
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Citations (9)
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| US6046266A (en) * | 1998-09-24 | 2000-04-04 | The Goodyear Tire & Rubber Company | Tire with silica reinforced tread and/or sidewall components |
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| CN104987552A (en) * | 2015-07-24 | 2015-10-21 | 山东玲珑轮胎股份有限公司 | Semi-steel transition layer sizing material and preparation method thereof |
| JP2016023207A (en) * | 2014-07-17 | 2016-02-08 | 東洋ゴム工業株式会社 | Side reinforced rubber composition for run flat tire and run flat tire |
| CN110128713A (en) * | 2019-06-05 | 2019-08-16 | 青岛森麒麟轮胎股份有限公司 | Anti-slippery hovercar tire tread formula and anti-slippery hovercar tire |
| CN110804223A (en) * | 2019-11-12 | 2020-02-18 | 寿光福麦斯轮胎有限公司 | Run-flat tire sidewall support rubber and preparation method thereof |
| CN111995801A (en) * | 2020-07-15 | 2020-11-27 | 山东玲珑轮胎股份有限公司 | Supporting rubber composition |
| CN112980062A (en) * | 2021-01-28 | 2021-06-18 | 北京玲珑轮胎有限公司 | Run-flat tire and rubber composition of support rubber thereof |
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2021
- 2021-12-02 CN CN202111461435.2A patent/CN114213722A/en active Pending
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| US6046266A (en) * | 1998-09-24 | 2000-04-04 | The Goodyear Tire & Rubber Company | Tire with silica reinforced tread and/or sidewall components |
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| JP2016023207A (en) * | 2014-07-17 | 2016-02-08 | 東洋ゴム工業株式会社 | Side reinforced rubber composition for run flat tire and run flat tire |
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| WO2021169602A1 (en) * | 2020-02-26 | 2021-09-02 | 山东玲珑轮胎股份有限公司 | High-modulus low-heat-generating support rubber composition |
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Non-Patent Citations (1)
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| 王慧;庄儒彬;姜辉;仇培超;韩绍楠;: "空气阻止剂NM360在半钢子午线轮胎过渡层胶中的应用", 橡胶科技, no. 05, pages 36 - 38 * |
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