CN111571844A - Preparation method of low rolling resistance tread rubber - Google Patents
Preparation method of low rolling resistance tread rubber Download PDFInfo
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- CN111571844A CN111571844A CN202010559458.6A CN202010559458A CN111571844A CN 111571844 A CN111571844 A CN 111571844A CN 202010559458 A CN202010559458 A CN 202010559458A CN 111571844 A CN111571844 A CN 111571844A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/22—Component parts, details or accessories; Auxiliary operations
- B29B7/28—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control
- B29B7/283—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control measuring data of the driving system, e.g. torque, speed, power
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
- B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/22—Component parts, details or accessories; Auxiliary operations
- B29B7/28—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/22—Component parts, details or accessories; Auxiliary operations
- B29B7/28—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control
- B29B7/286—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control measuring properties of the mixture, e.g. temperature, density
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7466—Combinations of similar mixers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/82—Heating or cooling
- B29B7/823—Temperature control
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/82—Heating or cooling
- B29B7/826—Apparatus therefor
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- 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
- B60C1/0016—Compositions of the tread
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/06—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
- B29B7/10—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary
- B29B7/18—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft
- B29B7/183—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft having a casing closely surrounding the rotors, e.g. of Banbury type
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The invention provides a preparation method of low rolling resistance tread rubber, which comprises the following steps: mixing the rubber materials in a series banburying manner to obtain master batch; mixing the master batch, a vulcanizing agent and an accelerator, and then vulcanizing to obtain tread rubber; the rubber material comprises the following components: the rubber component, carbon black, silicon dioxide, a silicon dioxide dispersing agent, processing oil, a silane coupling agent, a plasticizer, an active agent and a defense component; the rubber material comprises 100 parts by weight of rubber component and 60-120 parts by weight of silicon dioxide; the silicon dioxide dispersing agent is a mixture of saturated and unsaturated fatty acid zinc soaps. Under the condition of not changing the rubber component and the structure of the silicon dioxide, the invention can increase the dispersibility of the silicon dioxide in the rubber material, improve the processability of the rubber, greatly improve the wear resistance, the grip performance and the like of the tire, has lower cost and is beneficial to industrial application.
Description
Technical Field
The invention relates to the technical field of tire rubber, in particular to a preparation method of low rolling resistance tread rubber.
Background
The function of the tire comprises supporting the total mass of the vehicle, ensuring the adhesion of the wheel to the road surface and the like; according to the position of the tyre, the outer cover is composed of a tread, a cushion layer, a cord fabric layer, a tire bead and the like. The tread is the part of the tire contacting with the road surface, and the tread rubber, namely the outermost layer of rubber material of the tire, has good wear resistance, strength and low heat build-up during running. The tread rubber is mainly prepared by raw rubber such as natural rubber, butadiene rubber and the like, and a large amount of carbon black and other rubber additives.
Generally, the addition of a high content of silica to a rubber composition for a tread is one of the methods of reducing the rolling resistance of a tire. However, silica has a property of agglomeration during rubber processing, and is liable to cause a problem of difficulty in processability. In this regard, the use of highly dispersible silicas (modification of the silica structure) or modified rubbers (modification of the rubber structure properties) to improve the processability of the silicas in the rubber has been proposed by those skilled in the art.
The above prior art improves the processability by changing the property structure of silica or rubber, and the method increases the raw material cost a lot, and is low in economy, and not beneficial to industrial application.
Disclosure of Invention
In view of the above, the application provides a preparation method of a tread rubber with low rolling resistance, and the method can be used for preparing the tread rubber with low rolling resistance, and is simple and convenient to process and low in cost.
The invention provides a preparation method of low rolling resistance tread rubber, which comprises the following steps:
mixing the rubber materials in a series banburying manner to obtain master batch;
mixing the master batch, a vulcanizing agent and an accelerator, and then vulcanizing to obtain tread rubber;
the rubber material comprises the following components: the rubber component, carbon black, silicon dioxide, a silicon dioxide dispersing agent, processing oil, a silane coupling agent, a plasticizer, an active agent and a defense component;
the rubber material comprises 100 parts by weight of rubber component and 60-120 parts by weight of silicon dioxide; the silicon dioxide dispersing agent is a mixture of saturated and unsaturated fatty acid zinc soaps.
Preferably, the rubber material comprises the following components in parts by weight: 5-20 parts of carbon black; 0.5-5 parts of a silicon dioxide dispersing agent; 10-20 parts of processing oil; 6-12 parts of a silane coupling agent; 2-6 parts of a plasticizer; 1-8 parts of an active agent; 0.1-7 parts of a defense component;
the rubber component is selected from one or more of natural rubber, styrene-butadiene rubber and butadiene rubber.
Preferably, the plasticizer is a petroleum resin; the active agents include: 1-5 parts of stearic acid and 1-3 parts of zinc oxide.
Preferably, the aging component is selected from one or more of age resister 6PPD, age resister RD and protective wax.
Preferably, the defence components include: 1.5-2.5 parts of protective wax; 0.2-2 parts of age inhibitor 6 PPD; 0.2-2 parts of an anti-aging agent RD.
Preferably, the dropping point of the silica dispersant is 97 to 107 ℃.
Preferably, the speed of the rotors in the series internal mixing is 15-55 rpm, and the temperature of the cooling water is 15-25 ℃.
Preferably, the mixing process of the series internal mixing specifically comprises the following steps: after the internal mixing of the upper layer is finished, the rubber material enters the lower layer for constant-temperature internal mixing, and the master batch is obtained after discharging;
the upper top bolt pressure for upper layer banburying is 35-55N/cm2(ii) a The temperature of constant-temperature banburying is 145-150 ℃, and the time is 180-360 seconds.
Preferably, the promoter is selected from one or more of promoter CBS and promoter DPG.
Preferably, the vulcanization is carried out by using Banbury mixing equipment, the rotating speed of a rotor is 20-25 rpm, and the top plug pressure is 35-40N/cm2。
Compared with the prior art, the tread rubber with reduced rolling resistance is obtained by adding high-content silicon dioxide in the tread rubber formula, simultaneously adopting a saturated and unsaturated fatty acid zinc soap mixture as a dispersing aid of rubber materials, combining a mixing mode of series banburying and vulcanizing. Under the condition of not changing the rubber component and the structure of the silicon dioxide, the invention can increase the dispersibility of the silicon dioxide in the rubber material, improve the processability of the rubber, greatly improve the wear resistance, the grip performance and the like of the tire, has lower cost and is beneficial to industrial application.
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 preparation method of low rolling resistance tread rubber, which comprises the following steps:
mixing the rubber materials in a series banburying manner to obtain master batch;
mixing the master batch, a vulcanizing agent and an accelerator, and then vulcanizing to obtain tread rubber;
the rubber material comprises the following components: the rubber component, carbon black, silicon dioxide, a silicon dioxide dispersing agent, processing oil, a silane coupling agent, a plasticizer, an active agent and a defense component;
the rubber material comprises 100 parts by weight of rubber component and 60-120 parts by weight of silicon dioxide; the silicon dioxide dispersing agent is a mixture of saturated and unsaturated fatty acid zinc soaps.
The method can prepare the tread rubber with lower rolling resistance, has simple and convenient processing and lower cost, and is beneficial to industrial application.
According to a certain weight ratio, the tread rubber formula composition in the embodiment of the invention can comprise: 100 parts of rubber component, 60-120 parts of silicon dioxide, 5-20 parts of carbon black, 0.5-5 parts of silicon dioxide dispersing agent, 10-20 parts of processing oil, 6-12 parts of silane coupling agent, 2-6 parts of plasticizer, 1-8 parts of activator, 0.1-7 parts of aged component, 1-5 parts of vulcanizing agent and 0.2-7 parts of accelerator.
The rubber formula composition is also called a rubber material, wherein the embodiment of the invention adopts the conventional rubber component without carrying out chemical modification on the conventional rubber component. The rubber component can be one or more of natural rubber, styrene butadiene rubber and butadiene rubber; the rubber is prepared by mixing Natural Rubber (NR), Butadiene Rubber (BR) and styrene-butadiene rubber (SBR) in any proportion, such as NR10-30 parts, BR20-30 parts and SBR50-60 parts (preferably 10: 30: 60), and other weight proportions can be adopted.
Wherein the natural rubber is a natural high molecular compound taking polyisoprene as a main component, and is universal rubber with the widest application; the glue can be made into tobacco flakes, air-dried films, crepes and the like according to different glue making methods. The smoked sheet rubber is the most representative variety in natural rubber, generally classified according to the appearance into special grade, first grade, second grade, third grade, fourth grade and fifth grade. The market has domestic first-class standard glue SCR5 and imported smoked sheet glue RSS3, and the domestic first-class standard glue SCR5 is also commonly called No. 5 standard glue; the imported tabstock RSS3 implements "quality and packaging international standards for natural rubber grades" (green book) (1979 edition) "established by the international conference on rubber quality and packaging. In the examples of the present invention, the source of the natural rubber is not particularly limited, and commercially available products are used.
The styrene butadiene rubber is also called styrene butadiene copolymer, styrene butadiene rubber and the like, is the most common synthetic rubber variety and has better comprehensive performance. According to the polymerization method, the method can be divided into emulsion polymerization styrene-butadiene rubber, solution polymerization styrene-butadiene rubber and the like. In the embodiment of the present invention, the source of the styrene butadiene rubber is not particularly limited, and commercially available SBR of HP850 type or the like may be used. Cis-butadiene rubber is short for cis-1, 4-polybutadiene rubber and is mainly prepared by polymerizing monomer butadiene under the action of a catalyst, wherein the catalyst comprises cobalt series, nickel series, rare earth series (neodymium series) and the like. Compared with natural rubber and styrene butadiene rubber, the butadiene rubber has the characteristics of high elasticity, good wear resistance, good cold resistance, low heat generation and the like. The rare earth-based butadiene rubber, such as the commercial product having the model number CB24, is preferably used in the present invention.
In the present invention, the rubber composition can be used to reduce the rolling resistance of a tire by adding a high content of silica. Namely, the rubber material comprises 60-120 parts by weight of silica, preferably 75-110 parts, and more preferably 80-105 parts. The silica in the rubber material is white carbon black which mainly refers to precipitated silica, fumed silica, ultrafine silica gel and the like. The invention does not need to chemically modify the silicon dioxide, and the silicon dioxide with the conventional performance in the field can be adopted. Wherein the pH value of the silicon dioxide is 6-7; the white carbon black in the embodiment of the invention can be a commercial product with the model number of 1165MP, and the CTAB specific surface area is 145.0-170.0 g/cm3。
The rubber material comprises 5-20 parts of carbon black, preferably 6-15 parts, such as 8/10/15 parts. Carbon black, also known as carbon black, is an amorphous carbon, black powder; it has the main reinforcing function in rubber and can be divided into several varieties of high wear resistance, reinforcement, semi-reinforcement and the like. The carbon blacks used in the present invention are conventional in the art; in the embodiment of the invention, high wear-resistant carbon black can be adopted, and the nitrogen adsorption specific surface area (NSA) is 114-124 m2In g, as carbon black N234 product.
Because of the adoption of high-content silicon dioxide and the like, the invention takes the mixture of saturated and unsaturated fatty acid zinc soap as the dispersing auxiliary agent of the rubber material, can improve the mixing processability of rubber, promotes the white smoke dispersion in the rubber material, and can effectively improve the molyny of the rubber material. The invention preferably adopts 0.5-5 parts of silicon dioxide dispersant, more preferably 1-5 parts; such as excessive addition, tend to affect performance and economics. The degree of unsaturation of a zinc soap of fatty acids can be characterized by the iodine number, the greater the degree of unsaturation. The embodiment of the invention mainly adopts the silicon dioxide dispersing agent sold in the market, such as a product Disperaid-4A; the dropping point of the silicon dioxide dispersing agent is 97-107 ℃. The application uses an ASTM D566 test method to test and obtain the temperature of the dropping point; the dropping point is also called as a dropping point, and refers to the temperature (DEG C) at which the first drop of a solid or viscous substance begins to drop after the solid or viscous substance is heated and melted in a dropping point tester.
The rubber material provided by the embodiment of the invention comprises the components of processing oil, a silane coupling agent, a plasticizer and the like, and the processing and use performance of the rubber material are ensured. Wherein the processing oil is preferably 15 to 20 parts by weight; the present invention preferably employs commercially available, environmentally friendly oils such as product V500 oil. The silane coupling agent is a low-molecular organic silicon compound, and the weight part of the silane coupling agent is preferably 6-8 parts; the invention preferably employs a silane coupling agent Si-69, which is chemically bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide.
In a specific embodiment of the present invention, the plasticizer is petroleum resin, and the weight part of the plasticizer is preferably 3 to 5 parts. The petroleum resin is also called as hydrocarbon resin, and is a thermoplastic resin produced by the processes of pretreatment, polymerization, distillation and the like of C5 and C9 fractions which are byproducts of petroleum cracking. Petroleum resins are generally classified into C5 aliphatic and C9 aromatic, and mainly used rubbers are C5 petroleum resins having a low softening point and C5/C9 copolymer resins. Illustratively, in some embodiments of the invention, the petroleum resin is a commercially available 373N product having a softening point of 84 ℃ to 95 ℃.
In an embodiment of the invention, the rubber mass comprises: 1-8 parts of an active agent, 1-5 parts of a vulcanizing agent and 0.2-7 parts of an accelerator. The active agent can be divided into inorganic and organic, and is beneficial to reactions such as vulcanization and the like; in a preferred embodiment of the present invention, the active agent includes 1 to 5 parts of Stearic Acid (SA) and 1 to 3 parts of zinc oxide (ZnO). The vulcanizing agent is generally sulfur (S), and the weight part of the vulcanizing agent is preferably 1.2-3.5 parts. The accelerator is a vulcanization accelerator, and the embodiment of the invention can adopt a combination of an accelerator CBS and an accelerator DPG, wherein the chemical name of the accelerator CBS is N-cyclohexyl-2-benzothiazole sulfenamide, the chemical name of the accelerator DPG is 1, 3-diphenyl guanidine, and the mass ratio of the accelerator CBS to the accelerator DPG is 2-2.5: 1.5-1.8.
In addition, the rubber material preferably comprises 0.1-7 parts by weight of a defense component. The components of the old protection system can be divided into inorganic and organic, and mainly comprise old protection system substances such as an anti-aging agent, a paraffin product and the like. In a particular embodiment of the invention, the aging component is selected from one or more of age resister 6PPD, age resister RD and protective wax. Preferably, the defense components include: 1.5-2.5 parts of protective wax, 0.2-2 parts of antioxidant 6PPD and 0.2-2 parts of antioxidant RD; for example, 2 parts of protective wax, 1 part of antioxidant RD and 2 parts of antioxidant 6 PPD.
Wherein, the anti-aging agent refers to a chemical substance capable of delaying or inhibiting the aging process of the rubber product; can be divided into amines, phenols, heterocycles and other anti-aging agents according to chemical structures. The invention preferably adopts an amine antioxidant, specifically, the antioxidant can be selected from one or more of antioxidant 6PPD and antioxidant RD, and more preferably, the antioxidant is used in a compound way. The chemical name of the antioxidant 6PPD is N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine; the antioxidant RD is the trade name of the antioxidant 2,2, 4-trimethyl-1, 2-dihydroquine polymer. The substances used for physical aging prevention of rubber are mainly paraffins, and paraffin products generally used include: normal paraffin, microcrystalline paraffin and protective wax; ordinary paraffin is a substance separated from paraffin distillate oil by a simple process, microcrystalline paraffin is usually separated from residual oil left in a distillation still by a solvent separation method, and protective wax is a mixed substance blended from various paraffin components and a modified additive.
According to the invention, when the rubber formula is adopted, the series one-step method banburying equipment is used for mixing, the moly of the rubber material after one-step mixing can meet the use requirement, and the master batch is difficult to obtain by processing with a Banbury mixer or an open mill.
The series internal mixing equipment provided by the embodiment of the invention can be the existing series internal mixing equipment in the field; the series internal mixing equipment generally comprises an upper auxiliary machine and a lower auxiliary machine, and the mixing process of series internal mixing is as follows: after the internal mixing of the upper layer is finished, the rubber material enters the lower layer for constant-temperature internal mixing, and the rubber material is discharged to obtain the master (mixing) rubber.
In the embodiment of the invention, the rotor speed of the internal mixer used for series internal mixing can be 15-55 rpm, and the top plug pressure is 35-55N/cm2(ii) a The cooling water temperature of the internal mixer can be 15-25 ℃. The specific operation comprises the following steps: adding rubber components, white carbon black, a silane coupling agent, a rubber active agent, a rubber anti-aging agent, a plasticizer, a silicon dioxide dispersing agent and the like into an upper auxiliary machine, and pressing a top plug to heat the rubber material to 140 ℃; lifting the top plug, keeping for 10sec, pressing the top plug to make the temperature of the rubber material be 150 ℃, and discharging the rubber material to a lower auxiliary machine; heating the rubber material to 145-150 ℃ by a lower auxiliary machine, carrying out constant-temperature banburying for 180-360 seconds, and discharging the master rubber.
After the master batch is obtained, the master batch is added into Banbury mixing equipment, and sulfur and an accelerator are added for vulcanization to obtain the tread rubber. Wherein, the Banbury mixing equipment is well known in the field. The rotor speed of the internal mixer used for vulcanization can be 20-25 rpm, and the top plug pressure is 35-40N/cm2. In the vulcanization process, the rubber material is discharged when the temperature of the rubber material is between 100 ℃ and 110 ℃, and the final rubber compound is obtained.
The method can increase the dispersibility of the silicon dioxide in the rubber material without changing the rubber component and the structure of the silicon dioxide, improve the processability of the rubber, greatly improve the wear resistance, the grip performance and the like of the tire, and is low in cost and beneficial to industrial application.
For further understanding of the present application, the following describes a method for preparing a tread rubber with low rolling resistance provided in the present application with reference to examples. In the following examples, the manufacturers of the tandem one-shot internal mixers involved: Hanbourg-Freudenberger, internal mixer type: IM 320E, lower internal mixer model: and IM 550 ET.
Example 1
According to Table 1The formula (A) is mixed by using a series one-step internal mixer, the rotor speed of the internal mixer is 50rpm, and the top plug pressure is 50N/cm2The cooling water temperature is 25 ℃, and the concrete operation is as follows: adding rubber components, white carbon black, a silane coupling agent, a rubber active agent, a rubber anti-aging agent, a plasticizer, a silicon dioxide dispersing agent and the like into an upper auxiliary machine, and pressing a top plug to heat the rubber material to 140 ℃; lifting the top plug, keeping for 10sec, pressing the top plug to make the temperature of the rubber material be 150 ℃, and discharging the rubber material to a lower auxiliary machine; heating the rubber material to 150 ℃ by using a lower auxiliary machine, carrying out constant-temperature banburying for 180 seconds, and discharging the masterbatch.
Adding the obtained masterbatch into Banbury mixing equipment, adding sulfur and accelerator, wherein the rotating speed of the internal mixer is 25rpm, and the top plug pressure is 40N/cm2And vulcanizing, and discharging the rubber material at 105 ℃ to obtain the tread rubber.
TABLE 1 rubber formulations of the inventive examples
The PHR represents the percentage of the additive in the rubber product (rubber content in hundred).
In table 1, the sources of the components are as follows:
NR is RSS #3, a company from Hensheng Shanghai;
BR is CB24, manufacturer is LANXESS company;
SBR is HP850, and the manufacturer is JSR CORPORATION company;
the silicon dioxide dispersing agent is Disperaid-4A (D-4A for short), the component is a mixture of saturated and unsaturated fatty acid zinc soap, and the manufacturer is Ruboid Inc;
the silica is 1165MP, the manufacturer is Solvay fine chemical company, and the CTAB specific surface area is 145.0-170.0 g/cm3；
The coupling agent is Si69, and the manufacturer is Yingchuansamixing company;
the carbon black is N234, and the manufacturer is Zhonghua;
the environment-friendly Oil is V500 Oil, and the manufacturer is H & R GROUP company;
the petroleum resin is 373N, the manufacturer is EXXONMOBIL company, the softening point is 84-95 ℃;
the protective wax is OK2122H product, and the product is Yanggu Huatai chemical company with a solidifying point of 63-67 ℃.
Example 2
Tread rubbers were prepared according to the formulation of Table 1 by the method of example 1.
Comparative example
Tread rubbers were prepared according to the formulation of Table 1 by the method of example 1.
The tread rubber obtained above was subjected to a performance test, and the results were as follows.
TABLE 2 Performance Table for Tread rubber of the inventive examples
| Comparative example | Example 1 | Example 2 | |
| Mooney viscosity ML1+4 | 60 | 57 | 52 |
| Tanδ0℃ | 0.325 | 0.343 | 0.349 |
| Tanδ60℃ | 0.086 | 0.076 | 0.074 |
| Wear and tear | 0.36 | 0.35 | 0.34 |
Remarking:
mooney viscosity: conditional ML(1+4)100℃；
And (3) viscoelastic test: the test was performed using a UESHIMA instrument. The smaller the Tan60 ℃ value, the better the rubber rolling resistance. The higher the Tan0 deg.C value, the better the grip performance.
Testing the abrasion performance of rubber materials in a laboratory: the prepared sample is put into an abrasion instrument for testing, and the abrasion performance is poorer when the abrasion value is larger.
As is clear from the experimental results shown in Table 2, the addition of the silica dispersant D-4A can increase the silica content without affecting the processability of the rubber composition. The amount of the D-4A added is increased to increase the processability, so that the silica content can be increased according to the present invention. By increasing the amount of silica, the Tan0 ℃ was higher for the examples than for the comparative examples, and Tan60 ℃ was lower than for the comparative examples. Therefore, the invention improves the processability, and increases the content of silica to improve the rolling resistance and wet-grip performance of the rubber composition. It can also be seen from table 2 that the abrasion was higher in the comparative examples than in the examples, and therefore the abrasion was reduced in the overall formulation of the present invention.
The invention uses the silicon dioxide dispersing auxiliary agent and matches with a tandem one-step mixing process, so that the problem that the high-content silicon dioxide rubber composition is difficult to process is solved. The tread rubber obtained by the invention has low rolling resistance, remarkably improves the abrasion and the ground gripping performance of the tire, and can reduce the Moni by less than 10 units after being used. The method has the advantages of simple processing operation, low cost and contribution to application.
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 (10)
1. A preparation method of low rolling resistance tread rubber comprises the following steps:
mixing the rubber materials in a series banburying manner to obtain master batch;
mixing the master batch, a vulcanizing agent and an accelerator, and then vulcanizing to obtain tread rubber;
the rubber material comprises the following components: the rubber component, carbon black, silicon dioxide, a silicon dioxide dispersing agent, processing oil, a silane coupling agent, a plasticizer, an active agent and a defense component;
the rubber material comprises 100 parts by weight of rubber component and 60-120 parts by weight of silicon dioxide; the silicon dioxide dispersing agent is a mixture of saturated and unsaturated fatty acid zinc soaps.
2. The preparation method according to claim 1, wherein the rubber material comprises the following components in parts by weight: 5-20 parts of carbon black; 0.5-5 parts of a silicon dioxide dispersing agent; 10-20 parts of processing oil; 6-12 parts of a silane coupling agent; 2-6 parts of a plasticizer; 1-8 parts of an active agent; 0.1-7 parts of a defense component;
the rubber component is selected from one or more of natural rubber, styrene-butadiene rubber and butadiene rubber.
3. The production method according to claim 2, wherein the plasticizer is a petroleum resin; the active agents include: 1-5 parts of stearic acid and 1-3 parts of zinc oxide.
4. The method of claim 2, wherein the aging component is selected from one or more of age resister 6PPD, age resister RD and protective wax.
5. The method of claim 4, wherein the defense component comprises: 1.5-2.5 parts of protective wax; 0.2-2 parts of age inhibitor 6 PPD; 0.2-2 parts of an anti-aging agent RD.
6. The method according to any one of claims 1 to 5, wherein the silica dispersant has a dropping point of 97 ℃ to 107 ℃.
7. The preparation method according to claim 6, wherein the rotor speed of the serial internal mixing is 15-55 rpm, and the cooling water temperature is 15-25 ℃.
8. The preparation method according to claim 7, wherein the mixing process of the series internal mixing specifically comprises: after the internal mixing of the upper layer is finished, the rubber material enters the lower layer for constant-temperature internal mixing, and the master batch is obtained after discharging;
the upper top bolt pressure for upper layer banburying is 35-55N/cm2(ii) a The temperature of constant-temperature banburying is 145-150 ℃, and the time is 180-360 seconds.
9. The process of claim 2, wherein the promoter is selected from one or more of promoter CBS and promoter DPG.
10. The preparation method according to claim 2, wherein the vulcanization is carried out by a Banbury mixing device, the rotor speed is 20-25 rpm, and the plug-on pressure is 35-40N/cm2。
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| CN202010559458.6A CN111571844A (en) | 2020-06-18 | 2020-06-18 | Preparation method of low rolling resistance tread rubber |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113462049A (en) * | 2021-07-20 | 2021-10-01 | 正新橡胶（中国）有限公司 | Rubber composition for tire tread and preparation method thereof |
| CN113698680A (en) * | 2021-09-09 | 2021-11-26 | 正新橡胶（中国）有限公司 | Rubber composition, preparation method and application thereof |
| CN115572415A (en) * | 2022-10-09 | 2023-01-06 | 山东金宇轮胎有限公司 | Preparation method of low rolling resistance rubber material |
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| CN104119578A (en) * | 2014-07-17 | 2014-10-29 | 青岛双星轮胎工业有限公司 | Rubber composition for tread of truck radial tire with low hysteresis loss |
| CN105367831A (en) * | 2015-11-23 | 2016-03-02 | 赛轮金宇集团股份有限公司 | Low rolling-resistance high abrasion-resistance recap vulcanized tread rubber compound and preparation method thereof |
| CN105670065A (en) * | 2016-04-14 | 2016-06-15 | 中策橡胶集团有限公司 | Ultra-low rolling resistance tire tread rubber material, preparation method thereof and tires adopting same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104119578A (en) * | 2014-07-17 | 2014-10-29 | 青岛双星轮胎工业有限公司 | Rubber composition for tread of truck radial tire with low hysteresis loss |
| CN105367831A (en) * | 2015-11-23 | 2016-03-02 | 赛轮金宇集团股份有限公司 | Low rolling-resistance high abrasion-resistance recap vulcanized tread rubber compound and preparation method thereof |
| CN105670065A (en) * | 2016-04-14 | 2016-06-15 | 中策橡胶集团有限公司 | Ultra-low rolling resistance tire tread rubber material, preparation method thereof and tires adopting same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113462049A (en) * | 2021-07-20 | 2021-10-01 | 正新橡胶（中国）有限公司 | Rubber composition for tire tread and preparation method thereof |
| CN113698680A (en) * | 2021-09-09 | 2021-11-26 | 正新橡胶（中国）有限公司 | Rubber composition, preparation method and application thereof |
| CN115572415A (en) * | 2022-10-09 | 2023-01-06 | 山东金宇轮胎有限公司 | Preparation method of low rolling resistance rubber material |
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