CN112795059A - Low-odor rubber composition and tire - Google Patents
Low-odor rubber composition and tire Download PDFInfo
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- CN112795059A CN112795059A CN202110049619.1A CN202110049619A CN112795059A CN 112795059 A CN112795059 A CN 112795059A CN 202110049619 A CN202110049619 A CN 202110049619A CN 112795059 A CN112795059 A CN 112795059A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 78
- 239000005060 rubber Substances 0.000 title claims abstract description 78
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 39
- 239000004094 surface-active agent Substances 0.000 claims abstract description 36
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 34
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 23
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 20
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 20
- 229920001194 natural rubber Polymers 0.000 claims abstract description 20
- 239000006229 carbon black Substances 0.000 claims abstract description 19
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 239000013543 active substance Substances 0.000 claims abstract description 9
- 150000002646 long chain fatty acid esters Chemical class 0.000 claims abstract description 9
- 230000007123 defense Effects 0.000 claims abstract description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 23
- 235000021355 Stearic acid Nutrition 0.000 claims description 12
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 12
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 12
- 239000008117 stearic acid Substances 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 11
- 239000011787 zinc oxide Substances 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 238000010521 absorption reaction Methods 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
- 239000003112 inhibitor Substances 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- MUHFRORXWCGZGE-KTKRTIGZSA-N 2-hydroxyethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCO MUHFRORXWCGZGE-KTKRTIGZSA-N 0.000 claims description 3
- 239000004636 vulcanized rubber Substances 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000000704 physical effect Effects 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 15
- 238000004073 vulcanization Methods 0.000 description 12
- 239000001993 wax Substances 0.000 description 10
- STSDHUBQQWBRBH-UHFFFAOYSA-N n-cyclohexyl-1,3-benzothiazole-2-sulfonamide Chemical compound N=1C2=CC=CC=C2SC=1S(=O)(=O)NC1CCCCC1 STSDHUBQQWBRBH-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000009472 formulation Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000004200 microcrystalline wax Substances 0.000 description 3
- 235000019808 microcrystalline wax Nutrition 0.000 description 3
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical group C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- IEQAICDLOKRSRL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-dodecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO IEQAICDLOKRSRL-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000036314 physical performance Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000013040 rubber vulcanization Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- HNWAHFPYJHAAJE-UHFFFAOYSA-N n-tert-butyl-1,3-benzothiazole-2-sulfonamide Chemical compound C1=CC=C2SC(S(=O)(=O)NC(C)(C)C)=NC2=C1 HNWAHFPYJHAAJE-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- -1 polyoxyethylene dodecyl ether Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 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
- C08L7/00—Compositions of natural rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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 provides a low-odor rubber composition and a tire, wherein the rubber composition is prepared by mixing the following components: 30-70 parts by weight of natural rubber; 30-70 parts by weight of butadiene rubber; 45 to 70 parts by weight of carbon black; 3-8 parts by weight of an active agent; 1-4 parts by weight of tackifying resin; 5-12 parts by weight of a defense component; 0.5-2 parts by weight of a surfactant; 0.5-2 parts by weight of accelerator CBS; 3-6 parts by weight of sulfur; the surfactant is one or more of polyethylene glycol and polyethylene glycol long-chain fatty acid ester. The special surfactant is mainly added, when the tire is vulcanized, the surfactant can promote the reaction to form a uniform film on the surface of the rubber composition, inhibit odor components in the rubber from volatilizing, further reduce the odor, and do not influence the processing and physical properties of rubber materials. The rubber composition has low odor, can effectively improve the odor of the tire, and has good tire performance.
Description
Technical Field
The invention relates to the technical field of rubber products, in particular to a low-odor rubber composition and a tire.
Background
In daily life, a large number of rubber articles are filled, and the articles can generate strong odor due to the relationship of formulas and processes. With the improvement of the standard of life of people, the requirements on quality are more and more strict, and rubber products with strong odor are gradually not accepted by the market. Tires are mainly made of rubber materials, and tires with strong odor are gradually not accepted by the market. For example, the storage of tires on the ground in a warehouse, the storage of a vehicle compartment after spare tires, and the like generate a large amount of strong odor, and the human body feels uncomfortable. Within the tyre industry, the subjective assessment of odour rating is a minimum of 3 people rating odour, generally on a scale of 1 to 6, which in turn comprises: grade 1, no odor; grade 2, almost no odor; grade 3, very weak, mild odor; 4 grade, the smell can be easily felt; grade 5, very strong odor; grade 6, an intolerable odor has been reached.
At present, how to improve the odor of tires is an important issue in the industry. The way to suppress odor is to add aromatic substances such as essence and perfume into the rubber composition; or an odor adsorbent may be used in the formulation. Still other researchers have used changes in vulcanization accelerators, changing the ingredients of the formulation chemistry, to improve the odor of rubber compositions.
However, the above-mentioned prior methods are still in need of improvement in the level of odor without affecting the tire performance.
Disclosure of Invention
In view of the above, the present application provides a low-odor rubber composition and a tire, and the rubber composition provided by the present invention has a very low odor, can effectively improve the odor of the tire, and has good tire performance.
The invention provides a low-odor rubber composition which is prepared by mixing the following components:
30-70 parts by weight of natural rubber;
30-70 parts by weight of butadiene rubber;
45 to 70 parts by weight of carbon black;
3-8 parts by weight of an active agent;
1-4 parts by weight of tackifying resin;
5-12 parts by weight of a defense component;
0.5-2 parts by weight of a surfactant;
0.5-2 parts by weight of accelerator CBS;
3-6 parts by weight of sulfur;
the surfactant is selected from one or more of polyethylene glycol and polyethylene glycol long-chain fatty acid ester, and the molecular weight of the polyethylene glycol is 3000-5000.
Preferably, the polyethylene glycol long-chain fatty acid ester is selected from one or more of polyethylene glycol monooleate and polyethylene glycol dioleate.
Preferably, the vinyl content of the butadiene rubber is 1-3%, and the glass transition temperature is less than-100 ℃.
Preferably, the carbon black has an iodine absorption value of 78.0 to 88.0mgI2(ii)/g, oil absorption number is 67.0-77.0mL/100 g.
Preferably, the active agents include: 1.5-4 parts of zinc oxide and 1.5-4 parts of stearic acid.
Preferably, the defence components include: 1.5-4 parts of protective wax; 3.5-6 parts of age inhibitor 6 PPD; 0.1-2 parts of anti-aging agent RD.
Preferably, the rubber composition is prepared by mixing the following components: 30-70 parts by weight of natural rubber; 30-70 parts by weight of butadiene rubber; 45 to 70 parts by weight of carbon black; 1.5-4 parts by weight of zinc oxide; 1.5-4 parts by weight of stearic acid; 1-4 parts by weight of tackifying resin; 1.5-4 parts by weight of protective wax; 3.5-6 parts by weight of age inhibitor 6 PPD; 0.1-2 parts by weight of an antioxidant RD; 0.5-2 parts by weight of polyethylene glycol; 0.5-2 parts by weight of accelerator CBS; 3-6 parts of sulfur.
Preferably, the mixing comprises an internal mixing initial mixing stage and a final mixing stage, and the surfactant is added in the internal mixing initial mixing stage.
The present invention provides a tire comprising a vulcanizate of the low odor rubber composition described hereinbefore.
Compared with the prior art, the embodiment of the invention comprises, by weight, 30-70 parts of natural rubber, 30-70 parts of butadiene rubber, 45-70 parts of carbon black, 3-8 parts of an active agent and 1-4 parts of tackifying resin; 0.5-2 parts of surfactant and 5-12 parts of anti-aging component are subjected to banburying and primary mixing, the obtained rubber material, 3-6 parts of sulfur and 0.5-2 parts of accelerator CBS are mixed and then are subjected to trial refining and vulcanization, the surfactant is selected from one or more of polyethylene glycol and polyethylene glycol long-chain fatty acid ester, the molecular weight of the polyethylene glycol is 3000-5000, and the low-odor rubber composition is obtained. According to the invention, the specific surfactant is mainly added into the rubber formula, so that during the vulcanization reaction of the tire, the surfactant can promote the reaction to form a uniform film on the surface of the rubber composition, inhibit the volatilization of odor components in the rubber, further reduce the odor, and simultaneously, the processability and physical properties of the rubber material are not influenced. Therefore, the rubber composition provided by the invention has low odor, can effectively improve the odor of the tire, and has good tire performance.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. 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.
The invention provides a low-odor rubber composition which is prepared by mixing the following components:
30-70 parts by weight of natural rubber;
30-70 parts by weight of butadiene rubber;
45 to 70 parts by weight of carbon black;
3-8 parts by weight of an active agent;
1-4 parts by weight of tackifying resin;
5-12 parts by weight of a defense component;
0.5-2 parts by weight of a surfactant;
0.5-2 parts by weight of accelerator CBS;
3-6 parts by weight of sulfur;
the surfactant is selected from one or more of polyethylene glycol and polyethylene glycol long-chain fatty acid ester, and the molecular weight of the polyethylene glycol is 3000-5000.
In order to solve the problem of bad smell of tire rubber, the invention provides a low-smell rubber composition which does not influence the performance of tire rubber materials and can effectively improve the smell of tires.
In the formula of the low-odor rubber composition, the rubber components comprise 30-70 parts by weight of natural rubber and 30-70 parts by weight of butadiene rubber. The rubber composition preferably includes 40 to 60 parts by weight of natural rubber in parts by weight. Natural Rubber (NR) is a natural polymer compound containing polyisoprene as a main component, and is a general rubber which is most widely used; the natural rubber of the present invention is not particularly limited, and a commercially available product can be used.
In the embodiment of the present invention, natural rubber and butadiene rubber are used in combination, wherein the weight part of the butadiene rubber is preferably 40 to 60 parts. Butadiene rubber is a synthetic rubber mainly formed by polymerizing isobutene and a small amount of isoprene, and is abbreviated as BR in English. The type of the butadiene rubber is not particularly limited, and the preferable vinyl content is 1-3% by mass, and the glass transition temperature is less than-100 ℃. In a specific embodiment of the present invention, NR 50 parts and BR 50 parts may be used.
The rubber composition of the invention comprises 45-70 parts by weight of carbon black, preferably 50-60 parts by weight, and mainly plays a role in mechanical reinforcement. In the present invention, the type of the carbon black is not particularly limited, and commercially available carbon black for tires may be used. Preferably, carbon black N-326 is used, and the iodine absorption value is 78.0-88.0mgI2(ii)/g, oil absorption number is 67.0-77.0mL/100 g.
In the present invention, the rubber composition comprises 0.5 to 2 parts by weight of a surfactant, and preferably 0.6 to 1.5 parts by weight of a surfactant is used. The surfactant is selected from one or more of polyethylene glycol and polyethylene glycol long-chain fatty acid ester, preferably polyethylene glycol, and the molecular weight of the polyethylene glycol is 3000-5000. Wherein, the embodiment of the invention can be added with a small amount of PEG 4000N surfactant, and the effect is optimal; the surfactant PEG 4000N is a product sold in Sanyo chemical company, the molecular weight of the polyethylene glycol is 3500-4400, the freezing point is 53-54 ℃, and the water content is less than or equal to 1 wt%. The polyethylene glycol long-chain fatty acid ester has a fatty acid carbon number of 12 or more, for example, 15 to 20 carbon atoms, and is preferably one or more selected from polyethylene glycol monooleate and polyethylene glycol dioleate.
The surfactant used in the rubber composition of the present invention is a surfactant containing a specific hydrophobic group and a hydrophilic group; after use, the surfactant migrates to the surface layer of the tire to form a uniform film layer with the surface of the tire, such as an anti-aging agent, wax, oil, adhesive resin, and the like, wherein the hydrophobic groups of the polyethylene glycol surfactant are arranged on the rubber side, and the hydrophilic groups are arranged on the outside air side, so that the unevenness of the tire surface is reduced, the surface area is reduced, volatile odor substances with low molecular weight are dissolved in the film layer, the odor substances volatile in the air are reduced, and the generation of odor is suppressed.
Among them, the rubber composition using a small amount of polyethylene glycol as a surfactant has the lowest odor, and significantly improves the odor of tires. Meanwhile, after the surfactant is used, the processing performance and the physical performance of rubber materials are not influenced, and the tire can keep good performance.
TBBS (N-tertiary butyl-2-benzothiazole sulfonamide) is commonly used as a vulcanization accelerator in the existing rubber formula, but TBBS can generate amine odor, and a small amount of TBBS can cause people to feel uncomfortable. According to the invention, the accelerator and the surfactant are proportioned, and CBS (N-cyclohexyl-2-benzothiazole sulfonamide) is used as a vulcanization accelerator instead of TBBS, so that the generation of odor can be sufficiently reduced.
The rubber composition of the present invention comprises 0.5 to 2 parts by weight, preferably 0.6 to 1.5 parts by weight, for example, 0.7 part, 0.8 part, 0.9 part, 1.0 part, etc., of a vulcanization accelerator CBS. The surface active agent has certain activation influence on a rubber vulcanization system, and the consumption of the accelerator is properly reduced in the use process of the rubber vulcanization accelerator, so that scorching caused by too fast vulcanization of the rubber is avoided.
In the present invention, the low-odor rubber composition includes 3 to 8 parts of an active agent. The active agents preferably include: 1.5-4 parts of zinc oxide (ZnO) and 1.5-4 parts of stearic acid; the components of zinc oxide and stearic acid can play roles in lubrication, convenient processing, vulcanization promotion and the like. And, the rubber composition includes 1 to 4 parts by weight of a tackifying resin (tackifying resin); specifically, Escorez1102, petroleum resin and a softening point of 94-106 ℃ can be adopted. In the invention, 3-6 parts by weight of sulfur is adopted for vulcanization crosslinking reaction, and the sulfur is a common commercial vulcanizing agent.
The rubber composition comprises 5-12 parts of a defense component, and can be used in combination with physical defense and a chemical anti-aging agent. Preferably, the defense components include: 1.5-4 parts of protective wax; 3.5-6 parts of age inhibitor 6 PPD; 0.1-2 parts of anti-aging agent RD. The protective wax can be microcrystalline wax, and the carbon number distribution of C27-C46 is required to be 90 percent. The antioxidant 6PPD is N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine, preferably used in an amount of 3.6 to 5 parts by weight. The antioxidant 6PPD has good protection effect and high cost performance. The chemical name of the anti-aging agent RD is 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer, and the dosage is preferably 0.5-1.5 parts.
In a preferred embodiment of the present invention, the rubber composition is prepared by mixing the following components: 30-70 parts by weight of natural rubber; 30-70 parts by weight of butadiene rubber; 45 to 70 parts by weight of carbon black; 1.5-4 parts by weight of zinc oxide; 1.5-4 parts by weight of stearic acid; 1-4 parts by weight of tackifying resin; 1.5-4 parts by weight of protective wax; 3.5-6 parts by weight of age inhibitor 6 PPD; 0.1-2 parts by weight of an antioxidant RD; 0.5-2 parts by weight of polyethylene glycol; 0.5-2 parts by weight of accelerator CBS; 3-6 parts of sulfur.
The preparation method of the rubber composition provided by the embodiment of the invention specifically comprises the following steps:
preparing a master batch by primary mixing: sequentially adding the natural rubber raw rubber, the butadiene rubber, the carbon black, the zinc oxide, the stearic acid, the microcrystalline wax, the tackifying resin, the surfactant and the anti-aging agent into a Banbury mixer, carrying out banburying at 130 ℃ for 120 seconds, and discharging rubber at 160 ℃;
final mix preparation of final mix: the obtained master batch, sulfur, an accelerator and the like are added into an internal mixer, and the mixture can be discharged after being mixed for 120 seconds at 105 ℃ to obtain the rubber composition.
The rubber composition vulcanization conditions are as follows: the resulting mixture was heated at 160 ℃ for 20 minutes to prepare a physical test piece. The embodiment of the invention carries out performance verification and odor evaluation on the vulcanized rubber of the rubber composition, wherein the odor evaluation method comprises the following steps:
1. subjective rating method for odor
The experimental conditions are as follows: the samples were placed in an odor bottle at 25 ℃ ambient temperature and after 2 hours of standing the odor evaluation test was performed by 25 people. The odor rating scale is detailed in the following table (with a half-scale rating, e.g., 1.5/2.5/3.5/4.5/5.5):
TABLE 1 odor rating evaluation
| Grade 1-no odor |
| Class 2-almost odorless |
| Grade 3-very weak, slight odor |
| Grade 4-readily perceived odor |
| Grade 5-very strong odor |
| Grade 6-an intolerable odor has been reached |
2. Odor evaluation using an odor measuring apparatus XP-329 device
Calibrating an instrument: the odor measuring instrument XP-329 is used for zero calibration by sucking clean air;
the experimental conditions are as follows: the samples were placed in odor bottles at ambient temperature of 25 ℃ for 2 hours and subjected to odor evaluation tests. The instrument shows that higher values indicate higher odor levels (higher values, higher odor concentrations, and corresponding higher odor levels).
Embodiments of the present invention also provide a tire comprising a vulcanizate of the low odor rubber composition described above, which is primarily useful as a bead filler. The present invention is not particularly limited in terms of tire type, specification, and the like. The tire disclosed by the invention has the advantages of low odor and good performance.
For further understanding of the present application, the low-odor rubber composition and tire provided herein are specifically described below with reference to examples. It should be understood, however, that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention, which is defined by the following examples.
The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by manufacturers, and are all conventional products available on the market.
Example 1
According to the formula shown in the table 2, the raw natural rubber, the butadiene rubber, the carbon black, the zinc oxide, the stearic acid, the protective wax, the tackifying resin, the surfactant and the antioxidant are sequentially added into a Banbury mixer, mixed for 120 seconds at 130 ℃, and discharged at 160 ℃;
the obtained master batch, sulfur, an accelerator and the like were added to an internal mixer, and mixed at 105 ℃ for 120 seconds and then discharged to obtain a rubber composition.
Examples 2 to 3
According to the formulation of Table 2, a compound was prepared according to the procedure of example 1.
Comparative examples 1 to 2
According to the formulation of Table 3, a compound was prepared according to the procedure of example 1.
TABLE 2 formulation of rubber composition in examples of the present invention (in parts by weight)
| Components | Example 1 | Example 2 | Example 3 |
| NR | 50 | 50 | 50 |
| BR | 50 | 50 | 50 |
| Carbon black | 54 | 54 | 54 |
| ZnO | 3.0 | 3.0 | 3.0 |
| Stearic acid | 2.0 | 2.0 | 2.0 |
| Protective wax | 2.0 | 2.0 | 2.0 |
| Tackifying resins | 2.0 | 2.0 | 2.0 |
| Antioxidant 6PPD | 5.0 | 5.0 | 5.0 |
| Antiager RD | 0.5 | 0.5 | 0.5 |
| Ionet DO600 | 1.5 | - | - |
| Ionet PO600 | - | 1.5 | - |
| PEG 4000N | - | - | 1.5 |
| CBS | 0.8 | 0.8 | 0.8 |
| In.S | 3.5 | 3.5 | 3.5 |
TABLE 3 formulation of rubber composition in comparative examples of the present invention (in parts by weight)
| Components | Comparative example 1 | Comparative example 2 |
| NR | 50 | 50 |
| BR | 50 | 50 |
| Carbon black | 54 | 54 |
| Zinc oxide | 3.0 | 3.0 |
| Stearic acid | 2.0 | 2.0 |
| Protective wax | 2.0 | 2.0 |
| Tackifying resins | 2.0 | 2.0 |
| Antioxidant 6PPD | 5.0 | 5.0 |
| Antiager RD | 0.5 | 0.5 |
| Brij 35 | - | 1.5 |
| TBBS | 0.9 | - |
| CBS | - | 0.8 |
| In.S | 3.5 | 3.5 |
In tables 2 and 3, the source of the raw material components is as follows:
NR is Sync Shanghai company RSS # 3;
BR is butadiene rubber of a rubber part of a table, the grade is BR0150, the vinyl mass content is 2 percent, and the glass transition temperature is-101 ℃;
zinc oxide was obtained from Shandong Shunhua chemical company;
carbon Black N-326 from Shanghai cardBorter, iodine absorption value 78.0-88.0mgI2(iv)/g, oil absorption value 67.0-77.0mL/100 g;
stearic acid is SA from a Fengyi oil factory;
the protective wax is purchased from Ok2122H of Yanggu Huatai chemical company, and is microcrystalline wax, wherein the carbon number distribution of C27-C46 accounts for 90 percent;
the tackifying resin is Escorez1102, petroleum resin, and has a softening point of 94-106 ℃;
antioxidant 6PPD was obtained from Shandong Shunhua chemical company;
antioxidant RD was obtained from Shandong Shunhua chemical company;
brij 35 is polyoxyethylene dodecyl ether produced by Kanto chemical company, the melting point is 41-45 ℃, and the flash point is 190 ℃;
ionet DO600 was purchased from Sanyo chemical Co;
ionet PO600 was purchased from Sanyo chemical Co;
PEG 4000N is purchased from Sanyo chemical corporation, the molecular weight of the polyethylene glycol is 3500-4400, the freezing point is 53-54 ℃, and the water content is less than or equal to 1 percent;
TBBS was obtained from Shandong Shunhua chemical;
in.s was purchased from tin free washings.
The chemical formula of the main component of Ionet DO600 is as follows:
the Ionet PO600 comprises the following main components:
in the examples, the test conditions and the composition properties were verified as follows:
vulcanization conditions of the rubber composition: heating at 160 deg.C for 20 min to obtain test piece, and testing its performance. The performance results are as follows:
table 4 test performance results of comparative examples of the present invention
| Evaluation of | Comparative example 1 | Comparative example 2 |
| Elongation at Break EB (%) | 440 | 440 |
| HS (Shore hardness A) | 57 | 57 |
| MV | 53 | 48 |
| Evaluation of smell (25 persons) | 5.0 | 4.5 |
| Evaluation of smell (XP-329) | 1254 | 1168 |
Table 5 test performance results for inventive examples
| Evaluation of | Example 1 | Example 2 | Example 3 |
| Elongation at Break EB (%) | 430 | 430 | 430 |
| HS (Shore hardness A) | 56 | 57 | 57 |
| MV | 51 | 52 | 53 |
| Evaluation of smell (25 persons) | 4.0 | 4.0 | 3.5 |
| Evaluation of smell (XP-329) | 1081 | 1079 | 1012 |
Wherein, a USHIMA viscoelasticity tester measures Tan delta 60 ℃; the elongation at break test is in accordance with GB/T528-2009/ISO37: 2005; MV is Mooney viscosity and reflects the processability of the rubber material; the odor evaluation method was as described above.
According to tables 4 and 5, the rubber compound of the present invention has no change in the Mooney and hardness after the surfactant is used, which indicates that the addition of the surfactant has little influence on the processability of the rubber compound. Compared with the comparative example, the EB performance of the sizing material is basically unchanged after the surfactant is used, which shows that the physical performance of the sizing material is not influenced. Among them, the odor grade of the rubber composition using the surfactant PEG 4000N of the present invention, namely, the odor evaluation of 25 persons and the odor evaluation of XP-329 were the lowest. There is no specific national standard for tire odor grade, different automobile manufacturers provide corresponding standards according to their needs, and some automobile manufacturers require that the tire odor of tire suppliers is generally not higher than 4.0 grade.
According to the invention, the specific surfactant is mainly added into the rubber formula, so that odor components in the rubber are inhibited from volatilizing during vulcanization reaction of the tire, further the odor is reduced, and the processability and physical properties of the rubber material are not influenced. The invention can effectively improve the smell of the tire and ensure the good performance of the tire.
The above description is only a preferred embodiment of the present invention, and it should be noted that various modifications to these embodiments can be implemented by those skilled in the art without departing from the technical principle of the present invention, and these modifications should be construed as the scope of the present invention.
Claims (9)
1. A low-odor rubber composition is prepared by mixing the following components:
30-70 parts by weight of natural rubber;
30-70 parts by weight of butadiene rubber;
45 to 70 parts by weight of carbon black;
3-8 parts by weight of an active agent;
1-4 parts by weight of tackifying resin;
5-12 parts by weight of a defense component;
0.5-2 parts by weight of a surfactant;
0.5-2 parts by weight of accelerator CBS;
3-6 parts by weight of sulfur;
the surfactant is selected from one or more of polyethylene glycol and polyethylene glycol long-chain fatty acid ester, and the molecular weight of the polyethylene glycol is 3000-5000.
2. The low-odor rubber composition according to claim 1, wherein the polyethylene glycol long-chain fatty acid ester is selected from one or more of polyethylene glycol monooleate and polyethylene glycol dioleate.
3. The low-odor rubber composition according to claim 1, wherein the butadiene rubber has a vinyl content of 1 to 3% and a glass transition temperature of less than-100 ℃.
4. The low-odor rubber composition according to claim 1, wherein said carbon black has an iodine absorption value of 78.0 to 88.0mg I2(ii)/g, oil absorption number is 67.0-77.0mL/100 g.
5. The low odor rubber composition of claim 1 wherein said active agent comprises: 1.5-4 parts of zinc oxide and 1.5-4 parts of stearic acid.
6. The low odor rubber composition of claim 1 wherein said aged protection component comprises: 1.5-4 parts of protective wax; 3.5-6 parts of age inhibitor 6 PPD; 0.1-2 parts of anti-aging agent RD.
7. The low-odor rubber composition according to any one of claims 1 to 6, wherein the rubber composition is obtained by compounding: 30-70 parts by weight of natural rubber; 30-70 parts by weight of butadiene rubber; 45 to 70 parts by weight of carbon black; 1.5-4 parts by weight of zinc oxide; 1.5-4 parts by weight of stearic acid; 1-4 parts by weight of tackifying resin; 1.5-4 parts by weight of protective wax; 3.5-6 parts by weight of age inhibitor 6 PPD; 0.1-2 parts by weight of an antioxidant RD; 0.5-2 parts by weight of polyethylene glycol; 0.5-2 parts by weight of accelerator CBS; 3-6 parts of sulfur.
8. The low-odor rubber composition according to any one of claims 1 to 6, wherein said mixing comprises an internal mixing initial stage and a final mixing stage, and said surfactant is added in the internal mixing initial stage.
9. A tire characterized by comprising a vulcanized rubber of the rubber composition according to any one of claims 1 to 8.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3214122A1 (en) * | 2014-11-28 | 2017-09-06 | Sumitomo Rubber Industries, Ltd. | Rubber composition for tire outer layer, and pneumatic tire |
| CN107446194A (en) * | 2017-09-11 | 2017-12-08 | 青岛双星轮胎工业有限公司 | The passenger car spare tyre of low odor dispersion |
| CN107513190A (en) * | 2017-09-11 | 2017-12-26 | 青岛双星轮胎工业有限公司 | The passenger car spare tyre of low odor dispersion |
| CN108276626A (en) * | 2018-02-08 | 2018-07-13 | 厦门正新橡胶工业有限公司 | Low smell tyre stock and preparation method thereof |
| CN109401089A (en) * | 2018-11-20 | 2019-03-01 | 中策橡胶集团有限公司 | A kind of rubber composition and its tire for low smell tire |
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- 2021-01-14 CN CN202110049619.1A patent/CN112795059A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3214122A1 (en) * | 2014-11-28 | 2017-09-06 | Sumitomo Rubber Industries, Ltd. | Rubber composition for tire outer layer, and pneumatic tire |
| CN107446194A (en) * | 2017-09-11 | 2017-12-08 | 青岛双星轮胎工业有限公司 | The passenger car spare tyre of low odor dispersion |
| CN107513190A (en) * | 2017-09-11 | 2017-12-26 | 青岛双星轮胎工业有限公司 | The passenger car spare tyre of low odor dispersion |
| CN108276626A (en) * | 2018-02-08 | 2018-07-13 | 厦门正新橡胶工业有限公司 | Low smell tyre stock and preparation method thereof |
| CN109401089A (en) * | 2018-11-20 | 2019-03-01 | 中策橡胶集团有限公司 | A kind of rubber composition and its tire for low smell tire |
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Application publication date: 20210514 |