CN113801383A - Tire tread rubber material capable of improving thermal-oxidative aging resistance of tire tread and tire side - Google Patents
Tire tread rubber material capable of improving thermal-oxidative aging resistance of tire tread and tire side Download PDFInfo
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- CN113801383A CN113801383A CN202110932320.0A CN202110932320A CN113801383A CN 113801383 A CN113801383 A CN 113801383A CN 202110932320 A CN202110932320 A CN 202110932320A CN 113801383 A CN113801383 A CN 113801383A
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- 230000032683 aging Effects 0.000 title claims abstract description 51
- 229920001971 elastomer Polymers 0.000 title abstract description 23
- 239000005060 rubber Substances 0.000 title abstract description 23
- 239000000463 material Substances 0.000 title abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 241000208688 Eucommia Species 0.000 claims abstract description 13
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 5
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 5
- 229920001194 natural rubber Polymers 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 229920003051 synthetic elastomer Polymers 0.000 claims abstract description 4
- 239000005061 synthetic rubber Substances 0.000 claims abstract description 4
- 239000006229 carbon black Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 230000003712 anti-aging effect Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000004073 vulcanization Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 238000005299 abrasion Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 4
- 241000208689 Eucommia ulmoides Species 0.000 description 14
- 239000013074 reference sample Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 150000001336 alkenes Chemical group 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000000025 natural resin Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 241001520299 Phascolarctos cinereus Species 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 long-chain fatty acid modified phenolic resin Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000005671 trienes Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
The invention relates to a tread rubber material capable of improving the thermal-oxidative aging resistance of a tire tread and a tire side. The rubber material comprises the following raw material components: 20-50 parts of natural rubber, 50-80 parts of synthetic rubber and 1-10 parts of eucommia resin. Has the advantages that: the invention can effectively improve important mechanical properties after aging, such as tensile strength, tear strength, cutting resistance, Akron abrasion and the like, and can improve tan delta at 0 ℃ and reduce tan delta at 60 ℃.
Description
Technical Field
The invention relates to a tread rubber material capable of improving the thermal-oxidative aging resistance of a tire tread and a tire side.
Background
The thermal oxidation aging resistance of the exposed rubber part of the tire directly influences the use safety of the tire, and in general, some anti-aging agents are added into the rubber to improve the thermal oxidation aging resistance, but experiments show that even if the anti-aging agents are introduced, the mechanical properties of the anti-aging agents are greatly reduced after thermal oxidation aging, so that a new method is needed to be found to relieve the great reduction of the important mechanical properties after thermal oxidation aging. Patent CN101759892 mentions that introducing koala resin into agricultural tires can greatly improve the strong elongation after aging; patent CN102101926B also mentions that the introduction of a mixture containing alkyl-phenol resin, benzofuran-indene resin and olefin resin into the tire inner liner can improve the thermal oxidative aging resistance of the inner liner; patent CN103665285B points out that the aging resistance of rubber materials can be improved and the service life of rubber products can be prolonged by adopting long-chain fatty acid modified phenolic resin containing triene or conjugated trienoic acid; patent CN103665331B mentions that an olefin-modified phenol-DCPD-resin can improve the tear strength, resistance to thermo-oxidative aging and abrasion resistance of rubber. The above patents all mention the effect of resin on improving the thermal-oxidative aging resistance of rubber, and these resins are characterized by improving the thermal-oxidative aging resistance of rubber through chemical modification or by using several types of resins in a mixed manner.
Disclosure of Invention
Based on the defects of the prior art, the invention provides a tread rubber material capable of improving the thermal oxidation aging resistance of the tire tread and the tire side.
A tread compound capable of improving thermal-oxidative aging resistance of tire treads and sidewalls comprises the following raw material components: 20-50 parts of natural rubber, 50-80 parts of synthetic rubber and 1-10 parts of eucommia resin.
The raw material components of the rubber compound also comprise: 1-5 parts of zinc oxide, 1-4 parts of stearic acid, 20-120 parts of carbon black or white carbon black, 0.5-3 parts of an anti-aging agent, 1-4 parts of a vulcanization system and 0.5-3 parts of an accelerator.
The curing system is a peroxide curing system or a sulfur curing system.
Has the advantages that: the invention can effectively improve important mechanical properties after aging, such as tensile strength, tear strength, cutting resistance, Akron abrasion and the like, and can improve tan delta at 0 ℃ and reduce tan delta at 60 ℃.
Drawings
FIG. 1 is a graph comparing the dynamic ozone aging resistance of example 1 of the present invention and reference 1, wherein S0 is a graph of the dynamic ozone aging resistance of reference 1; s1 is a graph showing the dynamic ozone aging resistance of example 1.
Detailed Description
According to the invention, the eucommia resin is introduced into a tire side or tire tread formula according to a certain proportion, and the resin can effectively improve important mechanical properties after aging, such as tensile strength, tear strength, cutting resistance, Akron abrasion and the like.
The eucommia ulmoides resin is a natural resin extracted from eucommia ulmoides trees, is a mixture containing carboxylic acid groups, and long methylene and olefin chains, and has specific physical properties shown in the following table 1. 1-10 parts of eucommia resin is introduced into a tire tread or tire side formula in the form of an auxiliary agent, a common mixing process is adopted to meet the mixing requirement, an internal mixer or an open mill is used for mixing, the vulcanization temperature is controlled at 130-180 ℃ in the vulcanization process, and the vulcanization time is 10-60 minutes. The eucommia ulmoides resin is a mixed natural resin containing carboxylic acid groups, long chains of methylene, olefin and the like, and is introduced into a tire side or a tire tread formula according to a certain proportion, so that the resin can effectively improve important mechanical properties after aging, such as tensile strength, tear strength, cutting resistance, Akron abrasion and the like.
TABLE 1 physical parameters of eucommia ulmoides resin
| Appearance of the product | Blackish green color |
| Form of the composition | Tacky solid |
| Density (g/cm)3) | 0.94-0.98 |
| Softening temperature/. degree.C | 50-100 |
| Number average molecular weight | <7000 |
The eucommia ulmoides resin is a byproduct generated by extracting eucommia ulmoides rubber, has the characteristic of good compatibility with nonpolar rubber materials (such as butadiene rubber, styrene butadiene rubber and natural rubber), contains components with molecular weight from hundreds to thousands of different and contains double bonds, and the main mechanism of improving the aging resistance of rubber materials is as follows: the small molecular substance can migrate out of the surface to prevent oxygen from entering the rubber, and the large molecular component can be combined with the rubber to protect some rubber molecular chains from contacting with the oxygen, and the olefin-containing component can consume free radicals generated by aging. In addition, the eucommia ulmoides resource is a biological renewable resource, so that the eucommia ulmoides resin has the renewability. Thus, eucommia ulmoides resin is in a sense a bio-based renewable resin relative to synthetic resins.
Eucommia resin is prepared by mixing the following components in parts by weight per 100 parts of rubber: comprises natural rubber and synthetic rubber, 1-10 parts of eucommia resin is added, and other auxiliary agents are common auxiliary agents, such as: 1-5 parts of zinc oxide, 1-4 parts of stearic acid, 20-120 parts of carbon black or white carbon black, 0.5-3 parts of an anti-aging agent, 1-4 parts of a vulcanization system and 0.5-3 parts of an accelerator, and blending to obtain the eucommia resin modified carbon black system or white carbon black system blended rubber.
Example 1
Table 2 example 1 tread compound formula table
The results of mechanical property measurements before and after aging of example 1 are shown in Table 3.
TABLE 3 comparison of important mechanical Properties before and after aging
The experimental results in table 3 show that, compared with the reference sample, the eucommia resin has no obvious advantages in various mechanical properties before aging, but after aging, the eucommia resin has better elongation at break, tensile strength, tear strength, cutting resistance and Akron abrasion resistance than the reference sample, wherein the elongation at break, the cutting resistance index, the DIN abrasion index and the Akron abrasion index are obviously better than the reference sample. The introduction of the eucommia ulmoides resin can effectively prevent the mechanical property of the rubber composite material from being greatly reduced after aging.
The following table 4 shows the comparison of the tensile product and the aging coefficient, and the calculation formula of the tensile product and the aging coefficient is the ratio of the product of the tensile strength and the elongation at break after aging to the product of the tensile strength and the elongation at break before aging, and the larger the value, the better the aging resistance.
TABLE 4 comparison of aging resistance energy coefficients
| Sample (I) | Implement one | |
Reference sample 2 |
| Tensile product aging factor | 0.8542 | 0.7224 | 0.7952 |
As can be seen from Table 4, the eucommia ulmoides resin has the highest tensile product aging coefficient and is superior to the synthetic phenolic resin, and the application of the eucommia ulmoides resin to the tire tread aging resistance is proved.
Example 2
Table 5 example 2 tread compound formula table
Example 2 mechanical property profiles before and after aging are shown in table 6.
TABLE 6 comparison of important mechanical Properties before and after aging
As shown in the experimental results of Table 6, after aging, the Shore hardness of the reference sample is obviously increased, the elongation at break and the tear strength are greatly reduced, and after the eucommia resin is introduced, although the mechanical properties are also reduced, the elongation at break and the tear strength are obviously superior to those of the reference sample.
TABLE 7 comparison of tensile product aging coefficients
| Sample (I) | Example 2 | |
Reference sample 2 |
| Aging resistance energy coefficient | 0.7182 | 0.6326 | 0.6890 |
As shown in the experimental results of Table 7, the introduction of the eucommia ulmoides resin into the sidewall has the largest tensile volume aging coefficient, which is superior to that of the reference sample and the C5 resin. Proves the advantage of the eucommia ulmoides resin in resisting thermo-oxidative aging in the formula of the sidewall.
Dynamic ozone aging test
The test method comprises the following steps: GB/T13642; ozone concentration: 100 pphm; maximum elongation: 20 percent; aging period: 72 h; and (3) testing temperature: 40 ℃; and (3) stretching mode: dynamic state; stretching frequency: 0.5 Hz.
As can be seen from figure 1, after dynamic ozone aging, the edge surface of the reference sample generates obvious cracks, and after the eucommia resin is introduced, the length of the edge cracks is minimum, so that the eucommia resin introduced into the tire side formula has excellent aging resistance.
The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The above-described embodiments of the invention are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims, and not by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (3)
1. A tread compound capable of improving thermal-oxidative aging resistance of a tire tread and a tire sidewall is characterized by comprising the following raw material components: 20-50 parts of natural rubber, 50-80 parts of synthetic rubber and 1-10 parts of eucommia resin.
2. The tread compound of claim 1, wherein the raw components of the compound further comprise: 1-5 parts of zinc oxide, 1-4 parts of stearic acid, 20-120 parts of carbon black or white carbon black, 0.5-3 parts of an anti-aging agent, 1-4 parts of a vulcanization system and 0.5-3 parts of an accelerator.
3. The tread compound of claim 1, wherein the curing system is a peroxide curing system or a sulfur curing system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110932320.0A CN113801383A (en) | 2021-08-13 | 2021-08-13 | Tire tread rubber material capable of improving thermal-oxidative aging resistance of tire tread and tire side |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110932320.0A CN113801383A (en) | 2021-08-13 | 2021-08-13 | Tire tread rubber material capable of improving thermal-oxidative aging resistance of tire tread and tire side |
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|---|---|
| CN113801383A true CN113801383A (en) | 2021-12-17 |
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| CN202110932320.0A Pending CN113801383A (en) | 2021-08-13 | 2021-08-13 | Tire tread rubber material capable of improving thermal-oxidative aging resistance of tire tread and tire side |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977418A (en) * | 2012-11-15 | 2013-03-20 | 北京橡胶工业研究设计院 | Giant engineering machinery radial tire tread rubber composite used for mines |
| CN103254472A (en) * | 2012-02-21 | 2013-08-21 | 北京橡胶工业研究设计院 | All-steel truck radical tire tread rubber and tire using it |
| CN103421217A (en) * | 2013-08-20 | 2013-12-04 | 双星东风轮胎有限公司 | Rubber composite for wear-resistant tire treads |
| CN103435873A (en) * | 2013-09-02 | 2013-12-11 | 青岛中海嘉新材料有限公司 | Rubber composite for car radial tire treads |
| CN105713245A (en) * | 2016-01-30 | 2016-06-29 | 北京化工大学 | Bio-based reinforced plasticiser-eucommia ulmoides resin and preparation method thereof |
| CN111171396A (en) * | 2020-02-23 | 2020-05-19 | 广西玲珑轮胎有限公司 | Tread rubber material of tire for semi-steel ice-snow road surface |
| CN111171397A (en) * | 2020-02-26 | 2020-05-19 | 山东玲珑轮胎股份有限公司 | All-steel truck tread formula |
| WO2020243304A1 (en) * | 2019-05-29 | 2020-12-03 | Bridgestone Americas Tire Operations, Llc | Tire tread rubber composition and related methods |
| CN113004586A (en) * | 2019-12-19 | 2021-06-22 | 彤程化学（中国）有限公司 | Tire side wall rubber composition with low hysteresis loss and improved appearance and preparation method thereof |
-
2021
- 2021-08-13 CN CN202110932320.0A patent/CN113801383A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254472A (en) * | 2012-02-21 | 2013-08-21 | 北京橡胶工业研究设计院 | All-steel truck radical tire tread rubber and tire using it |
| CN102977418A (en) * | 2012-11-15 | 2013-03-20 | 北京橡胶工业研究设计院 | Giant engineering machinery radial tire tread rubber composite used for mines |
| CN103421217A (en) * | 2013-08-20 | 2013-12-04 | 双星东风轮胎有限公司 | Rubber composite for wear-resistant tire treads |
| CN103435873A (en) * | 2013-09-02 | 2013-12-11 | 青岛中海嘉新材料有限公司 | Rubber composite for car radial tire treads |
| CN105713245A (en) * | 2016-01-30 | 2016-06-29 | 北京化工大学 | Bio-based reinforced plasticiser-eucommia ulmoides resin and preparation method thereof |
| WO2020243304A1 (en) * | 2019-05-29 | 2020-12-03 | Bridgestone Americas Tire Operations, Llc | Tire tread rubber composition and related methods |
| CN113004586A (en) * | 2019-12-19 | 2021-06-22 | 彤程化学（中国）有限公司 | Tire side wall rubber composition with low hysteresis loss and improved appearance and preparation method thereof |
| CN111171396A (en) * | 2020-02-23 | 2020-05-19 | 广西玲珑轮胎有限公司 | Tread rubber material of tire for semi-steel ice-snow road surface |
| CN111171397A (en) * | 2020-02-26 | 2020-05-19 | 山东玲珑轮胎股份有限公司 | All-steel truck tread formula |
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