WO2015109791A1 - Rubber composition with natural rubber/carbon black and synthetic polyisoprene rubber/white carbon black as master batch and manufacturing process therefor - Google Patents

Rubber composition with natural rubber/carbon black and synthetic polyisoprene rubber/white carbon black as master batch and manufacturing process therefor Download PDF

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WO2015109791A1
WO2015109791A1 PCT/CN2014/082701 CN2014082701W WO2015109791A1 WO 2015109791 A1 WO2015109791 A1 WO 2015109791A1 CN 2014082701 W CN2014082701 W CN 2014082701W WO 2015109791 A1 WO2015109791 A1 WO 2015109791A1
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rubber
carbon black
parts
mass
masterbatch
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PCT/CN2014/082701
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French (fr)
Chinese (zh)
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王梦蛟
周宏斌
石超
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怡维怡橡胶研究院有限公司
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Publication of WO2015109791A1 publication Critical patent/WO2015109791A1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • B29B7/002—Methods
    • B29B7/005—Methods for mixing in batches
    • 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
    • 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
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2407/00—Characterised by the use of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • 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
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • 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

Definitions

  • the present invention relates to the field of rubber, and more particularly to the field of rubber products and rubber processing.
  • Energy loss in rubber during dynamic use is one of its basic characteristics, which is caused by rubber lag loss.
  • the hysteresis loss increases, the consumption and heat generation of the rubber compound increase during the dynamic deformation process, which causes the temperature of the rubber compound to rise, which in turn causes the strength and wear resistance of the rubber compound to decrease, resulting in early damage of tires and other products; more importantly, Increase tire rolling resistance, increase fuel consumption (fuel consumption), and increase carbon dioxide emissions.
  • Patent CN1539872A proposes a rubber formulation which is compatible with wet skid resistance and tire rolling resistance.
  • the composition of the composition is polyolefin and carbon black, white carbon black, and til silane.
  • the patent CN1141311A and the patent CN1141313A disclose a tread formulation in which a diene rubber is added to white carbon black and carbon black. The process is a conventional mixing process, and the filler and the auxiliary agent are added to the diene polymer for kneading.
  • Patent CN1134434A discloses elastomers, silica, carbon black compounds which have a carbon black content limit of less than 30 parts by mass and a combined ratio of silica to carbon black in the range of from 3/1 to 30/1.
  • Patent CN1140129A stipulates that the ratio of white carbon black/carbon black is at least 10:1, and the amount of carbon black is small, which is not good for wear resistance.
  • These patents all use the traditional mixing process. Carbon black/silica is added to the rubber together with the additives.
  • the carbon black/white carbon black inevitably needs non-rubber components such as adsorption aids, which reduces the combination of filler and rubber. It also reduces wear resistance.
  • the invention intends to design a rubber composition through a new mixing process, so that the carbon black/white carbon black is first combined with the rubber and then mixed with other rubber auxiliaries, and the ware is reduced in the premise of maintaining the wear resistance. Thermal properties improve the elasticity of the compound. Summary of the invention
  • an object of the present invention is to provide a rubber composition using natural rubber/carbon black, synthetic polyisoprene rubber/white carbon black as a masterbatch, and a processing technique thereof.
  • the use of solution to synthesize a polyisoprene polymer with a single component and a small non-rubber component, when preparing a synthetic polyisoprene white carbon When the black masterbatch is used, the surface of the white carbon black does not adsorb the rubber component, and the coupling agent acts to make the white carbon black better combined with the rubber, thereby improving the wear resistance and reducing the heat generation.
  • the rubber composition prepared in accordance with the teachings of the present invention, for use in a tire tread can reduce the heat build-up of the tire and the rolling resistance of the tire while maintaining wear resistance.
  • the present invention further relates to the following embodiments:
  • a rubber composition comprising natural oak carbon black and synthetic polyisoprene rubber J3 ⁇ 4/silica black masterbatch and a preparation process thereof, characterized in that:
  • Carbon black masterbatch process natural rubber and carbon black are mixed in an internal mixer to form carbon black masterbatch;
  • Silica black masterbatch process synthetic polyisoprene rubber and white carbon black, coupling agent is mixed in an internal mixer to form white carbon black masterbatch;
  • the carbon black masterbatch, the silica masterbatch, the antioxidant, the active agent, the accelerator, and the vulcanizing agent are kneaded in a composition ratio to prepare a rubber composition.
  • the ratio of the amount of the natural rubber to the synthetic polyisoprene rubber is 1:3-5:1 in terms of the total amount of the rubber, and the ratio of the carbon black/white carbon black is combined with the natural face.
  • the proportion of isoprene rubber is kept at a certain ratio, generally the ratio of the two fillers is kept consistent with the ratio of the two rubbers;
  • the total amount of carbon black and white carbon black is 5 to 120 parts by mass, preferably 10 to 100 parts by mass;
  • the carbon black masterbatch is used in an amount of 5 to 100 parts by weight of the natural rubber, preferably 3 to 4 parts by weight; and the white carbon black masterbatch is 100 parts by mass of the synthetic polyisoprene rubber.
  • the amount of white carbon black is 5 to 100 parts, preferably -80 parts, and the amount of the coupling agent is 0.5% by weight to 20% by weight of the white carbon black, preferably 1% by weight to 15% by weight ;
  • the natural rubber comprises a standard rubber, a gutta percha, a tobacco sheet glue, a silver inulin; wherein the synthetic polyisoprene rubber is a cis-polyisoprene rubber, a trans-polyisoprene rubber or a mixture of them.
  • the carbon black is any carbon black, preferably a carbon black having a surface area of 3 ⁇ 470-180 m 2 /g and a DBP absorption value of 60-150 (1 (T 5 m 3 /kg)).
  • leg white carbon black is any white carbon black, preferably precipitation method White carbon black having a specific surface area of 50 to 200 m 2 /g.
  • the coupling agent comprises the most commonly used bis(triethoxypropylsilane) tetrasulfide and disulfide, 3-thiocyanopropyl-triethoxysilane, ⁇ - a mercapto-trimethoxysilane, a zirconate coupling agent, a phthalate coupling agent, a nitro coupling agent, an alcohol compound, and the alcohol compound includes, but not limited to, propanol, butanol, ethylene glycol, Polyethylene glycol and its derivatives.
  • the activator is one or more of a combination of a metal oxide and a fatty acid and a fatty acid metal soap salt
  • the base metal oxide is one or more of zinc oxide, magnesium oxide, etc.
  • the salt is one or more of zinc stearate and zinc borate.
  • the antioxidant includes one or more of an amine antioxidant, a quinoline antioxidant, a benzimidazole antioxidant, and a protective wax.
  • the accelerator includes, but is not limited to, a sulfenamide accelerator, a thiazole accelerator, a granule, a steroid accelerator, or a combination thereof
  • the vulcanizing agent includes, but not limited to, sulfur, Insoluble sulfur, oil-filled sulfur, sulfur donor or a combination thereof.
  • the present invention also relates to a rubber compound or gel which is prepared according to the above preparation method.
  • the mixing process further involved in the present invention includes the following three process steps:
  • Carbon black masterbatch natural rubber and carbon black are mixed in any internal mixer, the rotation speed is 20-90 rpm, the mixing time is l-10min, and the rubber discharge is 3 ⁇ 43 ⁇ 4t less than 165 °C ;
  • White carbon black masterbatch Synthetic polyisoprene rubber and white carbon black and a certain amount of organic coupling agent are mixed in any internal mixer, $3 ⁇ 43 ⁇ 4 20-90 ⁇ , mixing time is l-10min, debinding The 3 ⁇ 43 ⁇ 4t control is lower than 170 ° C, and the mixing 3 ⁇ 43 ⁇ 4t is maintained at 130-165 ° C for 0.5-4 min ;
  • the carbon black masterbatch and the white carbon black masterbatch are mixed in an internal mixer for 0.5 min to 3 min according to the composition ratio, and then the activator, the anti-aging agent, etc. are added, and the mixing car is 20-90 rpm, and the kneading time is l- 10min ;
  • the masterbatch produced in the second step is kneaded with a vulcanizing agent and an accelerator in any internal mixer at a rotational speed of 1040 rpm and a mixing time of l-8 min.
  • the total amount of carbon black and white carbon black is from 5 to 120 parts by mass, preferably from 10 to 100 parts by mass, based on 100 parts by mass of the total amount of the rubber, wherein the carbon black is any carbon black.
  • the carbon black is any carbon black.
  • specific surface area of silica is preferably 50- 200 m 2 / g precipitated silica.
  • the ratio of natural rubber to synthetic polyisoprene rubber is 1:3 - 5:1.
  • the proportion of carbon black/white carbon black is generally the same as that of natural face synthetic polyisoprene rubber, and may be different.
  • the activator may be selected from zinc oxide, stearic acid, zinc stearate, magnesium oxide, zinc borate, etc., and the amount is generally 1-10 parts by mass, excellent; ⁇ 2-5 parts by mass; the antioxidant is p-phenylenediamine
  • the vulcanizing agent may be selected from ordinary sulfur powder, oil-filled sulfur, Insoluble sulfur, oil-insoluble, insoluble sulfur, etc., the amount of use is 0.2 to 10 parts by mass, preferably 5-5 parts by mass; and J is a promoter of rum and sulfenamide
  • the agent, the zinc carbamate type touch agent, the cockroach type touch agent or a combination thereof, the amount is generally ⁇ 0.2-8 parts by mass, preferably
  • Organosilane coupling agent X50S Contains 50% bis(3-ethylidene silane) tetrasulfide, containing 50% N330 carbon black, Evonik Iridium (Rizhao) Chemical Industry Co., Ltd.;
  • White carbon black 833MP Wuxi Hengcheng Co., Ltd.
  • Zinc Oxide Dalian Zinc Oxide Plant
  • Antioxidant 020 ⁇ -(1.3-dimethylbutyl)-indole,-phenyl-p-phenylenediamine, Jiangsu Shengao Chemical Technology Co., Ltd.;
  • Antioxidant RD 2,2,4-trimethyl-1, 2-dihydroquinoline polymer, Tianjin Kemai Auxiliary Co., Ltd.;
  • Protective wax Baimeirui 3 ⁇ 4 Chemicals (Suzhou) Co., Ltd.;
  • Promoter CZ ⁇ -cyclohexyl-2-benzothiazole sulfenamide, Shandong Shanghao Chemical Co., Ltd.; sulfur: Qingdao Jinyuling Industrial Co., Ltd.;
  • the amounts of the components in the following examples and comparative examples are parts by mass.
  • Formulation SMR2050; synthetic polyisoprene rubber IR 50; N234 carbon black 25; white carbon black 833MP25; silane coupling agent X50S 6; antioxidant RD 1.5; antioxidant 40202; zinc oxide 3; stearic acid 2; Wax 1; sulfur yellow 1; accelerator CZ 1.5.
  • a mixing process 50 parts by mass of SMR20 and 50 parts by mass of IR in a 90 rpm internal mixer, kneading for 60 seconds, adding a top plug to add 25 parts by mass of carbon black N234, 25 parts by mass of white carbon black 833MP, 6 parts by mass of silane coupling agent X50S, 1.5 parts by mass of antioxidant RD, 3 parts by mass of zinc oxide, 2 parts by mass of stearic acid, parts by mass of antioxidant 020, protective wax 1, and 60 seconds after compounding , cleaning, re-kneading for 90 seconds, the pressure mixing time is 210 seconds, and the glue is 3 ⁇ 43 ⁇ 4t l58 °C;
  • the final rubber mixing process 165.5 parts by mass of a batch of mixed masterbatch at the internal pressure of 60 rpm, after 30 seconds of mastication, the top plug is added with 1 part by mass of sulfur and 1.5 parts by mass of accelerator CZ; After 60 seconds of cleaning; after 30 seconds of mixing, the rubber is discharged, the pressure mixing time is 120 seconds, and the glue is 3 ⁇ 43 ⁇ 4t l03 ° C; Formulation: SMR20 50; Synthetic polyisoprene t-gel IR 50; N234 carbon black 25; Silica black 25; silane coupling agent X50S 6; antioxidant RD 1.5; antioxidant 4020 2; household wax 1; zinc oxide 3; stearic acid 2; sulfur 1;
  • Carbon black masterbatch process 50 parts by mass of SMR20 is added to the internal mixer at 90 rpm for 50 seconds, and the top plug is applied. 17 parts by mass of carbon black N234 is added, and the top plug is cleaned after 90 seconds of mixing. The remaining 8 parts by mass of carbon black N234 was poured into the mixture, and the top plug was cleaned for 30 seconds, and the topping was cleaned for 30 seconds; the pressure mixing time was 200 seconds, and the discharge temperature was 157 °C.
  • White carbon black masterbatch process 50 parts by mass of synthetic isoprene IR is injected into the internal mixer with a 90 rpm key, and after mixing for 50 seconds, the plug is added with 17 parts by mass of white carbon and 4 parts by mass of silane.
  • Coupling agent X50S after 60 seconds of mixing, put the top plug to add the remaining 8 parts by mass of silica and 2 parts by mass of silane coupling agent X50S; mix for 30 seconds, top plug cleaning, kneading for 60 seconds, and pressurizing and kneading The time is 200 seconds, and the glue is 3 ⁇ 43 ⁇ 4t l54 °C ;
  • Two-stage mixing process In a 90 rpm internal mixer, 75 parts of carbon black masterbatch and 81 parts by mass of silica black masterbatch were added, and the top plug was kneaded for 80 seconds, and 1.5 parts by mass of antioxidant RD and 2 parts by mass were added.
  • Antioxidant 4020 1 part by mass of protective wax, 3 parts by mass of zinc oxide, 2 parts by mass of stearic acid; 70 seconds of mixing; 30 seconds of rubber compounding; 180 seconds of pressure mixing time, 3 ⁇ 43 ⁇ 4t l53 °C ;
  • the elasticity was improved, the heat generation by compression was lowered, and the abrasion performance was improved, indicating that when the kneading process of the present invention was employed, the heat generation was lowered, the elasticity was improved, and the abrasion resistance was improved.
  • Formulation SMR20 100; N115 carbon black 20; white carbon black 30; silane coupling agent X50S 7.2; anti-aging agent RD 1.5; anti-aging agent column 2; protective wax 1; zinc oxide 3; stearic acid 2; sulfur 1; CZ 1.5.
  • a mixing process At $3 ⁇ 4! 100 parts by mass of 20# standard glue was added to the internal mixer of 90 rpm, and after 60 seconds of mastication, 20 parts by mass of carbon black N115, 30 parts by mass of white carbon black, 7.2 parts by mass of X50S, and 3 parts by mass of zinc oxide, 2 were added. Parts by mass stearic acid, 1.5 parts by mass of antioxidant RD, 2 parts by mass of antioxidant 020, 1 part by mass of protective wax, 60 seconds of mixing, topping 155 sweep, mixing 90 seconds of debinding, pressurizing mixing time For 210 seconds, the glue is 3 ⁇ 43 ⁇ 4t l63 °C.
  • Silica black masterbatch process 20 parts by mass of trans-polyisoprene and 40 parts by mass of cis-polyisoprene were vigorously introduced into an internal mixer of 90 rpm. After mixing for 50 seconds, add 20 parts by mass of silica and 4.8 parts by mass of no silane coupling agent X50S. After mixing for 80 seconds, lift the top plug and apply 10 parts by mass of silica and 2.4 parts by weight of silane. X50S, mixing for 0 seconds, lifting the top plug, mixing for 40 seconds; the pressure mixing time is 210 seconds, and the discharge temperature is 158 °C.
  • Trans isoprene TPI Mooney has high viscosity and is difficult to process.
  • cis isoprene with lower Mooney IR is used in combination with TPI, which have the same structural unit and good compatibility. Solved the 185 shortcomings of TPI processing difficulties.
  • the tensile strength and the tear strength of Example 2 were both higher than that of Comparative Example 2, and the temperature rise at the bottom of Example 2 was lower than that of Comparative Example 2, and the abrasion resistance was improved.
  • Formulation SMR20 ⁇ ; ⁇ 234 carbon black 30; white carbon black 20; silane coupling agent X50S 5; anti-aging agent RD 1.5; anti-aging agent shed 2; zinc oxide 3; stearic acid 2; sulfur yellow 1; accelerator CZ 1.5.
  • Two-stage process Add 164.5 parts by mass of a batch of mixed masterbatch in an internal mixer of 60 rpm. After mastication for 30 seconds, add a top plug to add 1 part by mass of sulfur and 1.5 parts by mass of accelerator CZ; mix for 60 seconds. After cleaning; after 30 seconds of mixing, the rubber is discharged, the pressure mixing time is 120 seconds, and the discharge temperature is 104 ° C;
  • Formulation SMR20 60; Synthetic polyisoprene rubber IR 40; N234 carbon black 30; Silica 20; Silane 200 coupling agent X50S 5; Antioxidant RD 1.5; Antioxidant 4020 2; Protective wax 1; ; stearic acid 2; sulfur yellow 1; accelerator CZ 1.5.
  • Carbon black masterbatch process 60 parts by weight of 20# standard glue is added to the internal mixer at 90 rpm, after 20 seconds of mastication, 20 parts by mass of carbon black N234 is added, and the top plug is cleaned for 80 seconds, and 10 mass is added.
  • the carbon black N234, 205 was mixed for 30 seconds to clean the top plug, and the rubber was mixed for 0 seconds.
  • the pressure mixing time was 200 seconds, and the rubber discharge temperature was 157 °C.
  • Silica black masterbatch process 40 parts by mass of trans-polyisoprene is synthesized in a 90 rpm internal mixer, and after mixing for 50 seconds, the plug is added with 13 parts by mass of white carbon black 833 ⁇ and 3.5 parts by mass.
  • a mixture of silane coupling agent X50S after 80 seconds of mixing, the top plug was cleaned, and a mixture of 7 parts by mass of white 833 ⁇ and 1.5 parts by mass of silane X50S was added, and the mixture was kneaded for 40 seconds, and the top plug was cleaned and kneaded for 0 seconds.
  • Discharge the pressurization mixing time is 210 seconds, and the discharge temperature is 210 degrees Celsius.
  • Example 3 has improved elasticity, reduced heat generation and improved wear performance, indicating that when the mixing process of the present invention is employed, heat generation is reduced, elasticity is improved, and abrasion resistance is improved. improve.

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  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

The main contents of the present invention are: pre-compounding a natural rubber/carbon black and a synthetic polyisoprene rubber/white carbon black to prepare a master batch, and then adding rubber auxiliaries according to a composition ratio to prepare a compounded rubber; and a manufacturing process. In the carbon black master batch of the composition, based on 100 parts by mass of the natural rubber, the amount of the carbon black used is 5 - 120 parts by mass, preferably 20 - 80 parts by mass, wherein the amount ratio of the natural rubber to the synthetic polyisoprene rubber is 1 : 3 - 5 : 1, the amount ratio of carbon black/white carbon black is kept within a certain ratio with respect to the amount ratio of natural rubber/synthetic polyisoprene rubber, and generally the ratio of the two fillers is kept consistent with the ratio of the two rubbers. A composition prepared by using the rubber composition of the present invention and the preparation process therefor has the advantages of good abrasion resistance, a high elasticity, and low heat generation, and can be used in the formulations for tyres as well as other rubber products.

Description

一种以天然橡胶 /炭黑、 合成聚异戊二烯橡胶 /白炭黑为母胶的橡胶组合物及 其加工工艺  Rubber composition using natural rubber/carbon black, synthetic polyisoprene rubber/white carbon black as masterbatch and processing technique thereof
领域 Field
本发明涉及橡胶领域， 特别涉及橡胶制品以及橡胶加工领域。  The present invention relates to the field of rubber, and more particularly to the field of rubber products and rubber processing.
背景: fcfe^ Background: fcfe^
橡胶在动态使用过程中能量损耗是其基本特征之一， 它是由胶料滞后损失导致的。 滞后损失增加时胶料在动态形变过程中倉遣消耗和生热增加，使胶料的温度上升，进而 使混炼胶的强度及耐磨性下降，造成轮胎等制品的早期损害；更重要的是增加轮胎的滚 动阻力， 增加燃料消耗（耗油量)， 增加二氧化碳的排放量。  Energy loss in rubber during dynamic use is one of its basic characteristics, which is caused by rubber lag loss. When the hysteresis loss increases, the consumption and heat generation of the rubber compound increase during the dynamic deformation process, which causes the temperature of the rubber compound to rise, which in turn causes the strength and wear resistance of the rubber compound to decrease, resulting in early damage of tires and other products; more importantly, Increase tire rolling resistance, increase fuel consumption (fuel consumption), and increase carbon dioxide emissions.
众多研究结果表明配方中使用补强性沉淀法二氧化硅填料可以降低轮胎的滚动阻 力。 专利 CN1539872A提出了一种抗湿滑性和轮胎滚动阻力相平衡的橡胶配方， 组合 物成分为聚烯烃与炭黑、 白炭黑、有 til硅烷。专利 CN1141311A以及专利 CN1141313A 公开了二烯烃橡胶加入白炭黑和炭黑的胎面配方，工艺为传统混炼工艺，将填料和助剂 加入二烯烃聚合物进行混炼。 专利 CN1134434A公开了弹性体、 二氧化硅、 炭黑胶料， 该专利对炭黑用量限制少于 30质量份，且二氧化硅与炭黑的并用比例为 3/1—30/1范围。 专利 CN1140129A规定白炭黑 /炭黑并用比例至少为 10:1， 炭黑用量少， 不利于耐磨。 这些专利都是采用传统混炼工艺， 炭黑 /白炭黑与助剂一同加入橡胶中， 炭黑 /白炭黑不 可避免要吸附助剂等非橡胶组分， 降低了填料与橡胶的结合， 同时也会降低耐磨性能。  Numerous studies have shown that the use of a reinforcing precipitation silica filler in the formulation can reduce the rolling resistance of the tire. Patent CN1539872A proposes a rubber formulation which is compatible with wet skid resistance and tire rolling resistance. The composition of the composition is polyolefin and carbon black, white carbon black, and til silane. The patent CN1141311A and the patent CN1141313A disclose a tread formulation in which a diene rubber is added to white carbon black and carbon black. The process is a conventional mixing process, and the filler and the auxiliary agent are added to the diene polymer for kneading. Patent CN1134434A discloses elastomers, silica, carbon black compounds which have a carbon black content limit of less than 30 parts by mass and a combined ratio of silica to carbon black in the range of from 3/1 to 30/1. Patent CN1140129A stipulates that the ratio of white carbon black/carbon black is at least 10:1, and the amount of carbon black is small, which is not good for wear resistance. These patents all use the traditional mixing process. Carbon black/silica is added to the rubber together with the additives. The carbon black/white carbon black inevitably needs non-rubber components such as adsorption aids, which reduces the combination of filler and rubber. It also reduces wear resistance.
本发明意在设计一种橡胶组合物通过新混炼工艺， 使炭黑 /白炭黑先与橡胶结合再 混入其它橡胶助剂， 倉^!多在保持耐磨的前提下降低胶料的生热性能， 提高胶料的弹性。 发明内容  The invention intends to design a rubber composition through a new mixing process, so that the carbon black/white carbon black is first combined with the rubber and then mixed with other rubber auxiliaries, and the ware is reduced in the premise of maintaining the wear resistance. Thermal properties improve the elasticity of the compound. Summary of the invention
针对现有技术问题，本发明的目的是提供一种以天然橡胶 /炭黑、合成聚异戊二 烯橡胶 /白炭黑为母胶的橡胶组合物及其加工工艺， 此工艺发明的创新在于利用溶 液合成聚异戊二烯聚合物成分单一，非橡胶组分少的优点， 当制备合成聚异戊二烯白炭 黑母胶时， 白炭黑表面不会吸附辆象胶组分， 再慰偶联剂作用，使白炭黑能够更好与 橡胶结合， 达到提高耐磨降低生热的目的。按照本发明技术制备的橡胶组合物，用于轮 胎胎面可以在保持耐磨性的前提下， 降低轮胎的生热和轮胎的滚动阻力。 In view of the prior art, an object of the present invention is to provide a rubber composition using natural rubber/carbon black, synthetic polyisoprene rubber/white carbon black as a masterbatch, and a processing technique thereof. The use of solution to synthesize a polyisoprene polymer with a single component and a small non-rubber component, when preparing a synthetic polyisoprene white carbon When the black masterbatch is used, the surface of the white carbon black does not adsorb the rubber component, and the coupling agent acts to make the white carbon black better combined with the rubber, thereby improving the wear resistance and reducing the heat generation. The rubber composition prepared in accordance with the teachings of the present invention, for use in a tire tread, can reduce the heat build-up of the tire and the rolling resistance of the tire while maintaining wear resistance.
本发明进一步涉及到如下实施方案： 一种含天然橡臉炭黑和合成聚异戊二烯橡 J¾/白炭黑母胶的橡胶组合物及制备工艺 ， 其特征在于：  The present invention further relates to the following embodiments: A rubber composition comprising natural oak carbon black and synthetic polyisoprene rubber J3⁄4/silica black masterbatch and a preparation process thereof, characterized in that:
母炼胶工艺：  Masterbatch process:
炭黑母胶工艺： 天然胶与炭黑在密炼机中混炼生成炭黑母胶；  Carbon black masterbatch process: natural rubber and carbon black are mixed in an internal mixer to form carbon black masterbatch;
白炭黑母胶工艺： 合成聚异戊二烯橡胶与白炭黑、 偶联剂在密炼机中混炼生成白 炭黑母胶；  Silica black masterbatch process: synthetic polyisoprene rubber and white carbon black, coupling agent is mixed in an internal mixer to form white carbon black masterbatch;
终炼胶工艺：  Final rubber mixing process:
将所述炭黑母胶、 白炭黑母胶、 防老剂、 活性剂、 促进剂、 硫化剂按组合物比例 混炼制备成橡胶组合物。  The carbon black masterbatch, the silica masterbatch, the antioxidant, the active agent, the accelerator, and the vulcanizing agent are kneaded in a composition ratio to prepare a rubber composition.
根据上述的制备方法， 以橡胶总用量 100质量份计， 天然橡胶与合成聚异戊二烯橡 胶的用量比为 1:3-5:1;炭黑 /白炭黑用量比例与天然臉合成聚异戊二烯橡胶的用量比例 保持一定比例，一般使两种填料的比例与两种橡胶比例保持一致；炭黑与白炭黑的总用 量为 5-120质量份， 优选 10-100质量份；  According to the above preparation method, the ratio of the amount of the natural rubber to the synthetic polyisoprene rubber is 1:3-5:1 in terms of the total amount of the rubber, and the ratio of the carbon black/white carbon black is combined with the natural face. The proportion of isoprene rubber is kept at a certain ratio, generally the ratio of the two fillers is kept consistent with the ratio of the two rubbers; the total amount of carbon black and white carbon black is 5 to 120 parts by mass, preferably 10 to 100 parts by mass;
根据上述的制备方法， 炭黑母胶以天然橡胶 100质量份计， 炭黑用量为 5-100份， 优 ¾-80份； 白炭黑母胶以合成聚异戊二烯橡胶 100质量份计， 白炭黑用量为 5-100份，优 -80份， 偶联剂用量为白炭黑的 0.5wt%-20wt%优选 lwt%— 15wt%; According to the above preparation method, the carbon black masterbatch is used in an amount of 5 to 100 parts by weight of the natural rubber, preferably 3 to 4 parts by weight; and the white carbon black masterbatch is 100 parts by mass of the synthetic polyisoprene rubber. , the amount of white carbon black is 5 to 100 parts, preferably -80 parts, and the amount of the coupling agent is 0.5% by weight to 20% by weight of the white carbon black, preferably 1% by weight to 15% by weight ;
根据上述的制备方法， 天然橡胶包括标准胶、杜仲胶、烟片胶、银菊胶； 其中合成 聚异戊二烯橡胶为顺式聚异戊二烯橡胶、 反式聚异戊二烯橡胶或它们的混合物。  According to the preparation method described above, the natural rubber comprises a standard rubber, a gutta percha, a tobacco sheet glue, a silver inulin; wherein the synthetic polyisoprene rubber is a cis-polyisoprene rubber, a trans-polyisoprene rubber or a mixture of them.
木艮据上述的制备方法，其中戶 炭黑为任意炭黑，优选 STSA比表面 ¾70-180m2/g ， 压^ DBP吸收值为 60-150(l(T5m3/kg)的炭黑； 腿白炭黑为任意白炭黑， 优选沉淀法 白炭黑， 比表面积为 50-200m2/g。 According to the above preparation method, the carbon black is any carbon black, preferably a carbon black having a surface area of 3⁄470-180 m 2 /g and a DBP absorption value of 60-150 (1 (T 5 m 3 /kg)). ; leg white carbon black is any white carbon black, preferably precipitation method White carbon black having a specific surface area of 50 to 200 m 2 /g.
根据上述的制备方法， 其中所述偶联剂包括最常用的双（三乙氧基丙基硅烷） 四 硫化物和二硫化物、 3-硫氰基丙基-三乙氧基硅烷、 γ -巯基-三甲氧基硅烷、 锆酸酯偶联 剂、酞酸酯偶联剂、硝基偶联剂、醇类化合物， 所述醇类化合物包括但不限于丙醇、 丁 醇、 乙二醇、 聚乙二醇及其衍生物。 木艮据上述，其中活化剂为金属氧化物和脂肪酸组合以及脂肪酸金属皂盐一种或多种 ， 戶; Μ金属氧化物为氧化锌、 氧化镁等一种或多种， 所述脂肪酸金属皂盐为硬脂酸锌、 硼酸锌等一种或多种。  According to the above preparation method, wherein the coupling agent comprises the most commonly used bis(triethoxypropylsilane) tetrasulfide and disulfide, 3-thiocyanopropyl-triethoxysilane, γ- a mercapto-trimethoxysilane, a zirconate coupling agent, a phthalate coupling agent, a nitro coupling agent, an alcohol compound, and the alcohol compound includes, but not limited to, propanol, butanol, ethylene glycol, Polyethylene glycol and its derivatives. According to the above, wherein the activator is one or more of a combination of a metal oxide and a fatty acid and a fatty acid metal soap salt; the base metal oxide is one or more of zinc oxide, magnesium oxide, etc., the fatty acid metal soap The salt is one or more of zinc stearate and zinc borate.
根据上述的制备方法， 其中防老剂包括胺类防老剂、喹啉类防老剂、苯并咪唑类防 老剂、 防护蜡一种或多种。  According to the above preparation method, the antioxidant includes one or more of an amine antioxidant, a quinoline antioxidant, a benzimidazole antioxidant, and a protective wax.
根据上述的橡胶组合物，其中促进剂包括但不限于次磺酰胺类促进剂、噻唑类促进 剂、禾烂姆类碰剂、胍类促进剂或它们的组合， 硫化剂包括但不限于硫黄、不溶性硫 黄、 充油硫黄、 硫黄给予体或它们的组合。  According to the above rubber composition, the accelerator includes, but is not limited to, a sulfenamide accelerator, a thiazole accelerator, a granule, a steroid accelerator, or a combination thereof, and the vulcanizing agent includes, but not limited to, sulfur, Insoluble sulfur, oil-filled sulfur, sulfur donor or a combination thereof.
本发明还涉及一种†艮据上述制备方法制备的混炼胶或 化胶。  The present invention also relates to a rubber compound or gel which is prepared according to the above preparation method.
本发明进一步涉及的混炼工艺包括如下三个工艺步骤：  The mixing process further involved in the present invention includes the following three process steps:
工艺步骤一：  Process step one:
炭黑母胶： 天然橡胶与炭黑在任一密炼机中混炼， 转速为 20-90rpm， 混炼时间为 l-10min, 排胶 ¾¾t小于 165°C; Carbon black masterbatch: natural rubber and carbon black are mixed in any internal mixer, the rotation speed is 20-90 rpm, the mixing time is l-10min, and the rubber discharge is 3⁄43⁄4t less than 165 °C ;
白炭黑母胶： 合成聚异戊二烯橡胶与白炭黑及一定量的有机偶联剂在任一密炼机 中混炼， $¾¾ 20-90φπι, 混炼时间为 l-10min， 排胶 ¾¾t控制低于 170°C， 混炼 ¾¾t 在 130-165°C下保持 0.5-4min; White carbon black masterbatch: Synthetic polyisoprene rubber and white carbon black and a certain amount of organic coupling agent are mixed in any internal mixer, $3⁄43⁄4 20-90φπι, mixing time is l-10min, debinding The 3⁄43⁄4t control is lower than 170 ° C, and the mixing 3⁄43⁄4t is maintained at 130-165 ° C for 0.5-4 min ;
工艺步骤二：  Process step two:
将炭黑母胶与白炭黑母胶按照组合物比例在密炼机中混合 0.5min-3min, 后力口入活 化剂、 防老剂等， 混炼车 20-90rpm， 混炼时间为 l-10min; 将歩骤二生产的母胶与硫化剂、 促进剂在任一密炼机中混炼， 转速为 1040rpm， 混炼时间为 l-8min。 本发明中所述橡胶组合物以橡胶总用量 100质量份计， 炭黑与白炭黑的总用量为 5-120质量份， 优选 10-100质量份， 其中所述炭黑为任意炭黑， 优选 STSA比表面积为 70-180m2/g的炭黑， 白炭黑优选比表面积为 50— 200 m2/g沉淀法白炭黑。 天然橡胶与合 成聚异戊二烯橡胶的用量比为 1:3— 5:1。炭黑 /白炭黑的用量比例与天然臉合成聚异戊二 烯橡胶的用量比例一般保持一致， 也可以不同。 The carbon black masterbatch and the white carbon black masterbatch are mixed in an internal mixer for 0.5 min to 3 min according to the composition ratio, and then the activator, the anti-aging agent, etc. are added, and the mixing car is 20-90 rpm, and the kneading time is l- 10min ; The masterbatch produced in the second step is kneaded with a vulcanizing agent and an accelerator in any internal mixer at a rotational speed of 1040 rpm and a mixing time of l-8 min. In the rubber composition of the present invention, the total amount of carbon black and white carbon black is from 5 to 120 parts by mass, preferably from 10 to 100 parts by mass, based on 100 parts by mass of the total amount of the rubber, wherein the carbon black is any carbon black. preferably STSA specific surface area of 70-180m 2 / g carbon black, specific surface area of silica is preferably 50- 200 m 2 / g precipitated silica. The ratio of natural rubber to synthetic polyisoprene rubber is 1:3 - 5:1. The proportion of carbon black/white carbon black is generally the same as that of natural face synthetic polyisoprene rubber, and may be different.
所述活化剂可选用氧化锌、 硬脂酸、 硬脂酸锌、 氧化镁、 硼酸锌等， 用量一般为 1-10质量份，优;^ 2-5质量份； 防老剂为对苯二胺类防老剂、喹啉类防老剂、苯并咪 唑类防老剂或其组合物， 总量不超过 8质量份， 优选 1-6质量份； 所述硫化剂可选用普通 硫黄粉， 充油硫黄， 不溶性硫黄， 充油不溶性硫黄等， 使用量按有效含量计， 一般用量 为 0.2-10质量份， 优选用嶽 5-5质量份； 删歸 J为禾烂姆类促进剂、 次磺酰胺类促 进剂、氨基甲酸锌类碰剂、胍类碰剂或它们的组合， 用量一般 Λ0.2-8质量份，优选 The activator may be selected from zinc oxide, stearic acid, zinc stearate, magnesium oxide, zinc borate, etc., and the amount is generally 1-10 parts by mass, excellent; ^ 2-5 parts by mass; the antioxidant is p-phenylenediamine The anti-aging agent, the quinoline anti-aging agent, the benzimidazole anti-aging agent or the combination thereof, the total amount is not more than 8 parts by mass, preferably 1-6 parts by mass; the vulcanizing agent may be selected from ordinary sulfur powder, oil-filled sulfur, Insoluble sulfur, oil-insoluble, insoluble sulfur, etc., the amount of use is 0.2 to 10 parts by mass, preferably 5-5 parts by mass; and J is a promoter of rum and sulfenamide The agent, the zinc carbamate type touch agent, the cockroach type touch agent or a combination thereof, the amount is generally Λ0.2-8 parts by mass, preferably
0.2-5质量份。 0.2-5 parts by mass.
具 施方式  Application method
下面用实施例进一步描述本发明， 但是本发明的范围不受这些实施例的限制。  The invention is further described by the following examples, but the scope of the invention is not limited by the examples.
表 1橡胶样品制备的仪器设备  Table 1 Equipment for the preparation of rubber samples
Figure imgf000005_0002
Figure imgf000005_0002
Figure imgf000005_0001
Figure imgf000005_0001
序  Preface
测试项目 测 示准 设备名称 规格型号 生产厂家 号  Test item Test standard Equipment name Specification model Manufacturer No.
1 硬度 GB T 531.1-2008 硬度计（邵 A) LX-A 上海六菱仪器厂 伺月画拉力实 1 Hardness GB T 531.1-2008 Hardness Tester (Shao A) LX-A Shanghai Liuling Instrument Factory Waiting for the moon
2 拉伸弓艘 GB T 528-2009 A1-3000 高铁检测仪器公司 验机  2 Stretch bow ship GB T 528-2009 A1-3000 High-speed rail testing equipment company
伺月画拉力实  Waiting for the moon
3 GB T 528-2009 A1-3000 高铁检测仪器公司 验机  3 GB T 528-2009 A1-3000 High-speed rail testing equipment company
伺月画拉力实  Waiting for the moon
4 扯断伸长率 GB T 528-2009 A1-3000 高铁检测仪器公司 验机  4 elongation at break GB T 528-2009 A1-3000 High-speed rail testing equipment company
5 回弹性 GB T 1681-2009 回弹性测试仪 GT-7042-RE 高铁检测仪器公司 5 Resilience GB T 1681-2009 Resilience Tester GT-7042-RE High-speed Rail Testing Equipment Company
6 疲劳生热 GB T 1687-1993 压缩生热 几 RH-2000N 高铁检测仪器公司6 Fatigue heat generation GB T 1687-1993 Compressed heat generation Several RH-2000N High-speed rail testing equipment company
7 7
DIN磨耗 GB-T9867-1988 DIN磨耗 佥机 GT-7012-D 高铁检测仪器公司 DIN wear GB-T9867-1988 DIN wear 佥 machine GT-7012-D high-speed rail testing equipment company
8 阿克隆磨耗¾¾佥 8 Acron wear 3⁄43⁄4佥
阿克隆磨耗 GB-T1689-1998 GT-7012-A 高铁检测仪器公司 机  Acron wear GB-T1689-1998 GT-7012-A high-speed rail testing equipment company
EPLEXOR  EPLEXOR
9 动态粘弹性¾¾佥 GB T9870.1-2006 动态粘弹谱仪 德国 GABO公司  9 Dynamic viscoelasticity 3⁄43⁄4佥 GB T9870.1-2006 Dynamic viscoelastic spectrometer Germany GABO
500N  500N
下列化学药品应用于实施例和对比例： The following chemicals were applied to the examples and comparative examples:
2嘛准胶： 马来西亚长发橡胶厂；  2May Glue: Malaysia Changfa Rubber Factory;
合成顺式聚异戊二烯 IR: 青岛伊科思新材料有限公司；  Synthesis of cis-polyisoprene IR: Qingdao Ikesi New Materials Co., Ltd.;
合成反式聚异戊二烯 TPI: 青岛第派新材料有限公司；  Synthesis of trans-polyisoprene TPI: Qingdao Dipai New Materials Co., Ltd.;
有机硅烷偶联剂 X50S:含有 50%双（3-乙襲丙基硅烷）四硫化物，含有 50%N330 炭黑， 赢创岚星（日照）化学工业有限公司；  Organosilane coupling agent X50S: Contains 50% bis(3-ethylidene silane) tetrasulfide, containing 50% N330 carbon black, Evonik Iridium (Rizhao) Chemical Industry Co., Ltd.;
N115, N234: 卡博特（中国）有限公司；  N115, N234: Cabot (China) Co., Ltd.;
白炭黑 833MP: 无锡恒诚 有限公司；  White carbon black 833MP: Wuxi Hengcheng Co., Ltd.;
氧化锌： 大连氧化锌厂；  Zinc Oxide: Dalian Zinc Oxide Plant;
硬脂酸： PF1808, 马来西亚立成有限公司；  Stearic acid: PF1808, Malaysia Licheng Co., Ltd.;
防老剂 020: Ν-(1.3-二甲基丁基) -Ν，-苯基对苯二胺，江苏圣奥化学科技有限公司； 防老剂 RD: 2,2,4-三甲基 -1,2-二氢化喹啉聚合物， 天津科迈助剂有限公司； 防护蜡： 百美瑞 ¾化学品 （苏州）有限公司；  Antioxidant 020: Ν-(1.3-dimethylbutyl)-indole,-phenyl-p-phenylenediamine, Jiangsu Shengao Chemical Technology Co., Ltd.; Antioxidant RD: 2,2,4-trimethyl-1, 2-dihydroquinoline polymer, Tianjin Kemai Auxiliary Co., Ltd.; Protective wax: Baimeirui 3⁄4 Chemicals (Suzhou) Co., Ltd.;
促进剂 CZ ： Ν-环己基 -2-苯并噻唑次磺酰胺， 山东尚舜化工有限公司； 硫黄： 青岛金玉棱实业有限公司； 以下实施例和对比例中的组分用量均为质量份。 Promoter CZ : Ν-cyclohexyl-2-benzothiazole sulfenamide, Shandong Shanghao Chemical Co., Ltd.; sulfur: Qingdao Jinyuling Industrial Co., Ltd.; The amounts of the components in the following examples and comparative examples are parts by mass.
对比例 1  Comparative example 1
配方： SMR2050; 合成聚异戊二烯橡胶 IR 50; N234炭黑 25; 白炭黑 833MP25; 硅烷偶联剂 X50S 6; 防老剂 RD 1.5; 防老剂 40202; 氧化锌 3; 硬脂酸 2; 防护蜡 1; 硫黄 1； 促进剂 CZ 1.5。  Formulation: SMR2050; synthetic polyisoprene rubber IR 50; N234 carbon black 25; white carbon black 833MP25; silane coupling agent X50S 6; antioxidant RD 1.5; antioxidant 40202; zinc oxide 3; stearic acid 2; Wax 1; sulfur yellow 1; accelerator CZ 1.5.
一段混炼工艺:在车 为 90rpm的密炼机中力口入 50质量份 SMR20和 50质量份 IR， 混炼 60秒， 提上顶栓加入 25质量份炭黑 N234、 25质量份白炭黑 833MP、 6质量份硅 烷偶联剂 X50S、 1.5质量份防老剂 RD、 3质量份氧化锌、 2质量份硬脂酸、 质量份防 老剂 020、 防护蜡 1， 混炼 60秒后提上顶栓， 清扫， 再混炼 90秒排胶， 加压混时间 为 210秒， 排胶 ¾¾t l58°C;  A mixing process: 50 parts by mass of SMR20 and 50 parts by mass of IR in a 90 rpm internal mixer, kneading for 60 seconds, adding a top plug to add 25 parts by mass of carbon black N234, 25 parts by mass of white carbon black 833MP, 6 parts by mass of silane coupling agent X50S, 1.5 parts by mass of antioxidant RD, 3 parts by mass of zinc oxide, 2 parts by mass of stearic acid, parts by mass of antioxidant 020, protective wax 1, and 60 seconds after compounding , cleaning, re-kneading for 90 seconds, the pressure mixing time is 210 seconds, and the glue is 3⁄43⁄4t l58 °C;
终炼胶混炼工艺：在转速为 60rpm的密炼机种力口入 165.5质量份一段混炼母胶，塑 炼 30秒后 顶栓加入 1质量份硫黄及 1.5质量份促进剂 CZ; 混炼 60秒后清扫； 混 炼 30秒后排胶， 加压混炼时间为 120秒， 排胶 ¾¾t l03°C; 配方： SMR20 50； 合成聚异戊二烯t胶 IR 50; N234炭黑 25; 白炭黑 25; 硅烷 偶联剂 X50S 6; 防老剂 RD 1.5; 防老剂 4020 2; 附户蜡 1; 氧化锌 3; 硬脂酸 2; 硫 黄 1; 碰剂 CZ 1.5。  The final rubber mixing process: 165.5 parts by mass of a batch of mixed masterbatch at the internal pressure of 60 rpm, after 30 seconds of mastication, the top plug is added with 1 part by mass of sulfur and 1.5 parts by mass of accelerator CZ; After 60 seconds of cleaning; after 30 seconds of mixing, the rubber is discharged, the pressure mixing time is 120 seconds, and the glue is 3⁄43⁄4t l03 ° C; Formulation: SMR20 50; Synthetic polyisoprene t-gel IR 50; N234 carbon black 25; Silica black 25; silane coupling agent X50S 6; antioxidant RD 1.5; antioxidant 4020 2; household wax 1; zinc oxide 3; stearic acid 2; sulfur 1;
一段混炼工艺：  A mixing process:
炭黑母胶工艺：在转速为 90rpm的密炼机中加入 50质量份 SMR20塑炼 50秒后提 上顶栓， 力口入 17质量份炭黑 N234, 混炼 90秒后 顶栓清扫， 力口入剩余 8质量份炭 黑 N234, 混炼 30秒提上顶栓清扫， 混炼 30秒排胶； 加压混炼时间为 200秒， 排胶温 度 157°C。  Carbon black masterbatch process: 50 parts by mass of SMR20 is added to the internal mixer at 90 rpm for 50 seconds, and the top plug is applied. 17 parts by mass of carbon black N234 is added, and the top plug is cleaned after 90 seconds of mixing. The remaining 8 parts by mass of carbon black N234 was poured into the mixture, and the top plug was cleaned for 30 seconds, and the topping was cleaned for 30 seconds; the pressure mixing time was 200 seconds, and the discharge temperature was 157 °C.
白炭黑母胶工艺：在车键为 90rpm的密炼机中力口入 50质量份合成异戊二烯 IR，混 炼 50秒后 顶栓加入 17质量份白炭黑及 4质量份硅烷偶联剂 X50S;混炼 60秒后提 上顶栓加入剩余 8质量份白炭黑及 2质量份硅烷偶联剂 X50S;混炼 30秒 顶栓清扫， 混炼 60秒排胶； 加压混炼时间为 200秒， 排胶 ¾¾t l54°C; White carbon black masterbatch process: 50 parts by mass of synthetic isoprene IR is injected into the internal mixer with a 90 rpm key, and after mixing for 50 seconds, the plug is added with 17 parts by mass of white carbon and 4 parts by mass of silane. Coupling agent X50S; after 60 seconds of mixing, put the top plug to add the remaining 8 parts by mass of silica and 2 parts by mass of silane coupling agent X50S; mix for 30 seconds, top plug cleaning, kneading for 60 seconds, and pressurizing and kneading The time is 200 seconds, and the glue is 3⁄43⁄4t l54 °C ;
二段混炼工艺： 在 为 90rpm的密炼机中力口入 75质 分炭黑母胶与 81质量份白炭黑母胶， 混 炼 80秒提上顶栓，力口入 1.5质量份防老剂 RD、 2质量份防老剂 4020、 1质量份防护蜡、 3质量份氧化锌、 2质量份硬脂酸； 混炼 70秒清扫； 再混炼 30秒排胶； 加压混炼时间 为 180秒， 排胶 ¾¾t l53°C; Two-stage mixing process: In a 90 rpm internal mixer, 75 parts of carbon black masterbatch and 81 parts by mass of silica black masterbatch were added, and the top plug was kneaded for 80 seconds, and 1.5 parts by mass of antioxidant RD and 2 parts by mass were added. Antioxidant 4020, 1 part by mass of protective wax, 3 parts by mass of zinc oxide, 2 parts by mass of stearic acid; 70 seconds of mixing; 30 seconds of rubber compounding; 180 seconds of pressure mixing time, 3⁄43⁄4t l53 °C ;
终炼胶混炼工艺：  Final rubber mixing process:
在车 为 60rpm的密炼机中力口入 165.5质量份二段混炼母胶， 混炼 30秒 f^i:顶栓 加 1质量份硫黄及 1.5质量份促进剂 CZ; 混炼 60秒清扫； 再混炼 30秒排胶， 加压混 炼时间为 120秒， 排胶 ¾¾t 105 °C。  In the mixer of 60 rpm, 165.5 parts by mass of two-stage mixing masterbatch was mixed, and mixing for 30 seconds f^i: top plug plus 1 part by mass of sulfur and 1.5 parts by mass of accelerator CZ; mixing for 60 seconds cleaning Re-kneading for 30 seconds, the pressure mixing time is 120 seconds, and the glue is 3⁄43⁄4t 105 °C.
表 3: 实施例 1和对比例 1的性能对比  Table 3: Performance comparison of Example 1 and Comparative Example 1
Figure imgf000008_0001
Figure imgf000008_0001
实施例 1与对比例 1相比， 弹性提高， 压缩生热降低， 磨耗性能提高， 说明当采 用本发明混炼工艺， 生热降低， 弹性提高， 耐磨性提高。  In the first embodiment, as compared with the comparative example 1, the elasticity was improved, the heat generation by compression was lowered, and the abrasion performance was improved, indicating that when the kneading process of the present invention was employed, the heat generation was lowered, the elasticity was improved, and the abrasion resistance was improved.
对比例 2  Comparative example 2
配方： SMR20 100; N115炭黑 20; 白炭黑 30; 硅烷偶联剂 X50S 7.2； 防老剂 RD 1.5; 防老剂欄 2; 防护蜡 1; 氧化锌 3; 硬脂酸 2; 硫黄 1; 碰剂 CZ 1.5。  Formulation: SMR20 100; N115 carbon black 20; white carbon black 30; silane coupling agent X50S 7.2; anti-aging agent RD 1.5; anti-aging agent column 2; protective wax 1; zinc oxide 3; stearic acid 2; sulfur 1; CZ 1.5.
一段混炼工艺： 在$¾！为 90rpm的密炼机中力口入 20#标准胶 100质量份，塑炼 60秒后加入 20质量 份炭黑 N115、 30质量份白炭黑、 7.2质量份 X50S、 3质量份氧化锌、 2质量份硬脂酸、 1.5质量份防老剂 RD、 2质量份防老剂 020、 1质量份防护蜡， 混炼 60秒提上顶栓清 155 扫， 混炼 90秒排胶， 加压混炼时间为 210秒， 排胶 ¾¾t l63°C。 A mixing process: At $3⁄4! 100 parts by mass of 20# standard glue was added to the internal mixer of 90 rpm, and after 60 seconds of mastication, 20 parts by mass of carbon black N115, 30 parts by mass of white carbon black, 7.2 parts by mass of X50S, and 3 parts by mass of zinc oxide, 2 were added. Parts by mass stearic acid, 1.5 parts by mass of antioxidant RD, 2 parts by mass of antioxidant 020, 1 part by mass of protective wax, 60 seconds of mixing, topping 155 sweep, mixing 90 seconds of debinding, pressurizing mixing time For 210 seconds, the glue is 3⁄43⁄4t l63 °C.
终炼胶混炼工艺：  Final rubber mixing process:
在转速为 60rpm的密炼机中力口入 166.7质量份一段母胶， 混炼 30秒后 f^i:顶栓加 入 1质量份硫黄、 1.5质量份 剂 CZ,， 混炼 60秒清扫， 再混炼 30秒排胶， 加压混 炼时间为 120秒， 排胶 ¾¾t为 98°C。  In a mixer with a rotation speed of 60 rpm, 166.7 parts by mass of a masterbatch was placed in the mouth, and after mixing for 30 seconds, f^i: the top plug was added with 1 part by mass of sulfur, 1.5 parts by mass of CZ, and the mixture was kneaded for 60 seconds, and then The mixture was kneaded for 30 seconds, the pressurization mixing time was 120 seconds, and the rubber discharge was 3⁄43⁄4t at 98 °C.
160 例 2 160 cases 2
配方： 2嘛准橡胶 0; 反式聚异戊二烯 TPI 20; 顺式聚异戊二烯 IR 40; N115 炭黑 20; 白炭黑 30; 硅烷偶联剂 7.2; 防老剂 RD 1.5; 防老剂 40202; 防护蜡 1; 氧 化锌 3; 硬脂酸 2; 硫黄 1; 促进剂 CZ 1.5。  Formulation: 2: quasi-rubber 0; trans-polyisoprene TPI 20; cis-polyisoprene IR 40; N115 carbon black 20; white carbon black 30; silane coupling agent 7.2; anti-aging agent RD 1.5; anti-aging Agent 40202; protective wax 1; zinc oxide 3; stearic acid 2; sulfur yellow 1; accelerator CZ 1.5.
一段混炼工艺：  A mixing process:
165 炭黑母胶工艺： 在转速为 90rpm的密炼机中加入 20#标准胶 0质量份， 塑炼 50 秒后加入 13质量份炭黑 N115, 混炼 80秒 顶栓清扫， 力口入 7质量份炭黑 N115, 混 炼 30秒提上顶栓清扫， 混炼 40秒排胶， 加压混炼时间为 200秒， 排胶 ¾¾t l65°C。  165 carbon black masterbatch process: Add 0# standard rubber 0 parts by mass in an internal mixer with a speed of 90 rpm, add 10 parts of carbon black N115 after 50 seconds of mastication, mix 80 seconds of top plug cleaning, and force into the 7 Mass parts of carbon black N115, mixing for 30 seconds, lifting the top plug, mixing for 40 seconds, mixing and mixing for 200 seconds, and discharging 3⁄43⁄4t l65 °C.
白炭黑母胶工艺:在车 为 90rpm的密炼机中力口入合成反式聚异戊二烯 20质量份、 顺式聚异戊二烯 40质量份。 混炼 50秒后 顶栓加入 20质量份白炭黑与 4.8质量份 no 硅烷偶联剂 X50S, 混炼 80秒后提上顶栓清扫， 力口入 10质量份白炭黑与 2.4质量份硅 烷 X50S, 混炼 0秒提上顶栓清扫， 混炼 40秒排胶； 加压混炼时间为 210秒， 排胶温 度为 158°C。  Silica black masterbatch process: 20 parts by mass of trans-polyisoprene and 40 parts by mass of cis-polyisoprene were vigorously introduced into an internal mixer of 90 rpm. After mixing for 50 seconds, add 20 parts by mass of silica and 4.8 parts by mass of no silane coupling agent X50S. After mixing for 80 seconds, lift the top plug and apply 10 parts by mass of silica and 2.4 parts by weight of silane. X50S, mixing for 0 seconds, lifting the top plug, mixing for 40 seconds; the pressure mixing time is 210 seconds, and the discharge temperature is 158 °C.
二段混炼工艺：  Two-stage mixing process:
在车 为 90rpm的密炼机中力口入 60质量份炭黑母胶，以及 97.2质量份白炭黑母胶， 175 混炼 60秒 顶栓加入 3质量份氧化锌、 2质量份硬脂酸、 1.5质量份防老剂 RD、 2 质量份防老剂 020、 1质量份防护蜡， 混炼 80秒清扫， 在混炼 30秒排出二段母胶， 加 压混炼时间为 170秒， 排胶 ¾¾t为 154°C。  60 parts by mass of carbon black masterbatch and 97.2 parts by mass of silica black masterbatch in a 90 rpm internal mixer, 175 kneading for 60 seconds, and 3 parts by mass of zinc oxide and 2 parts by mass of stearic acid. 1.5 parts by mass of anti-aging agent RD, 2 parts by mass of anti-aging agent 020, 1 part by mass of protective wax, mixing for 80 seconds, mixing two-stage masterbatch in mixing for 30 seconds, pressurizing mixing time is 170 seconds, discharging glue 3⁄43⁄4t It is 154 ° C.
终炼胶混炼工艺： 在转速为 60r/min的密炼机中力口入 166.7质量份二段母胶，混炼 30秒后^ :顶栓加 入 1质量份硫黄， 1.5质量份 剂 CZ,， 混炼 60秒清扫， 再混炼 30秒排胶， 加压混 炼时间为 120秒， 排胶 ¾¾t为 98°C。 Final rubber mixing process: In a mixer with a rotational speed of 60 r/min, 166.7 parts by mass of two-stage masterbatch was force-injected, and after mixing for 30 seconds, the top plug was added with 1 part by mass of sulfur, 1.5 parts by mass of CZ, and kneaded for 60 seconds. Re-kneading for 30 seconds, the pressure mixing time is 120 seconds, and the rubber discharge is 98 °C.
表 4: 实施例 2和对比例 2的性能对比  Table 4: Performance comparison of Example 2 and Comparative Example 2
Figure imgf000010_0001
Figure imgf000010_0001
反式异戊二烯 TPI门尼粘度高，加工困难，实施例 2中使用门尼较低的顺式异戊二 烯 IR与 TPI并用， 二者具有相同的结构单元， 相容性好， 同时解决了 TPI加工困难的 185 缺点。 实施例 2的拉伸强度、 撕裂强度均高于对比例 2， 实施例 2底部温升低于对比例 2， 磨耗性能提高。  Trans isoprene TPI Mooney has high viscosity and is difficult to process. In Example 2, cis isoprene with lower Mooney IR is used in combination with TPI, which have the same structural unit and good compatibility. Solved the 185 shortcomings of TPI processing difficulties. The tensile strength and the tear strength of Example 2 were both higher than that of Comparative Example 2, and the temperature rise at the bottom of Example 2 was lower than that of Comparative Example 2, and the abrasion resistance was improved.
对比例 3  Comparative example 3
配方： SMR20 ΐω; Ν234炭黑 30; 白炭黑 20;硅烷偶联剂 X50S 5;防老剂 RD 1.5; 防老剂棚 2; 氧化锌 3; 硬脂酸 2; 硫黄 1; 促进剂 CZ 1.5。 Formulation: SMR20 ΐω ; Ν234 carbon black 30; white carbon black 20; silane coupling agent X50S 5; anti-aging agent RD 1.5; anti-aging agent shed 2; zinc oxide 3; stearic acid 2; sulfur yellow 1; accelerator CZ 1.5.
190 一段混炼工艺： 在车键为 90rpm的密炼机中加入 100质量份 SMR20, 混炼 60秒， 提上顶栓加入 30质量份炭黑 N234、 20质量份白炭黑、 5质量份硅烷偶联剂 X50S、 1.5 质量份防老剂 RD、 3质量份氧化锌、 2质量份硬脂酸、 2质量份防老剂 020、 1质量份 防护蜡， 混炼 60秒后 顶栓， 清扫， 再混炼 90秒排胶， 总混时间为 210秒,排胶温 度 162°C; 190 One-stage mixing process: 100 parts by mass of SMR20 is added to an internal mixer with a 90 rpm key, kneaded for 60 seconds, and a top plug is added to add 30 parts by mass of carbon black N234, 20 parts by mass of white carbon black, and 5 parts by mass of silane. Coupling agent X50S, 1.5 parts by mass of antioxidant RD, 3 parts by mass of zinc oxide, 2 parts by mass of stearic acid, 2 parts by mass of antioxidant 020, 1 part by mass of protective wax, after 60 seconds of top plug, cleaning, remixing Refining the rubber for 90 seconds, the total mixing time is 210 seconds, and the temperature is discharged. Degree 162 ° C ;
195 二段工艺： 在繊为 60rpm的密炼机种加入 164.5质量份一段混炼母胶， 塑炼 30 秒后提上顶栓加入 1质量份硫黄及 1.5质量份促进剂 CZ; 混炼 60秒后清扫； 混炼 30 秒后排胶， 加压混炼时间为 120秒， 排胶温度 104°C;  195 Two-stage process: Add 164.5 parts by mass of a batch of mixed masterbatch in an internal mixer of 60 rpm. After mastication for 30 seconds, add a top plug to add 1 part by mass of sulfur and 1.5 parts by mass of accelerator CZ; mix for 60 seconds. After cleaning; after 30 seconds of mixing, the rubber is discharged, the pressure mixing time is 120 seconds, and the discharge temperature is 104 ° C;
«例3  «Example 3
配方： SMR20 60; 合成聚异戊二烯橡胶 IR 40; N234炭黑 30; 白炭黑 20; 硅烷 200 偶联剂 X50S 5; 防老剂 RD 1.5; 防老剂 4020 2; 防护蜡 1; 氧化锌 3; 硬脂酸 2; 硫 黄 1; 促进剂 CZ 1.5。  Formulation: SMR20 60; Synthetic polyisoprene rubber IR 40; N234 carbon black 30; Silica 20; Silane 200 coupling agent X50S 5; Antioxidant RD 1.5; Antioxidant 4020 2; Protective wax 1; ; stearic acid 2; sulfur yellow 1; accelerator CZ 1.5.
一段混炼工艺：  A mixing process:
炭黑母胶工艺： 在转速为 90rpm的密炼机中加入 20#标准胶 60质量份， 塑炼 50 秒后加入 20质量份炭黑 N234, 混炼 80秒提上顶栓清扫， 加入 10质量份炭黑 N234, 205 混炼 30秒 顶栓清扫， 混炼 0秒排胶， 加压混炼时间为 200秒， 排胶温度 157°C。  Carbon black masterbatch process: 60 parts by weight of 20# standard glue is added to the internal mixer at 90 rpm, after 20 seconds of mastication, 20 parts by mass of carbon black N234 is added, and the top plug is cleaned for 80 seconds, and 10 mass is added. The carbon black N234, 205 was mixed for 30 seconds to clean the top plug, and the rubber was mixed for 0 seconds. The pressure mixing time was 200 seconds, and the rubber discharge temperature was 157 °C.
白炭黑母胶工艺:在车 为 90rpm的密炼机中力口入合成反式聚异戊二烯 40质量份， 混炼 50秒后 顶栓加入 13质量份白炭黑 833ΜΡ与 3.5质量份硅烷偶联剂 X50S的混 合物，混炼 80秒后 顶栓清扫，力口入 7质量份白炭黑 833ΜΡ与 1.5质量份硅烷 X50S 的混合物， 混炼 40秒提上顶栓清扫， 混炼 0秒排胶； 加压混炼时间为 210秒， 排胶温 210 度为 153°C。  Silica black masterbatch process: 40 parts by mass of trans-polyisoprene is synthesized in a 90 rpm internal mixer, and after mixing for 50 seconds, the plug is added with 13 parts by mass of white carbon black 833 ΜΡ and 3.5 parts by mass. A mixture of silane coupling agent X50S, after 80 seconds of mixing, the top plug was cleaned, and a mixture of 7 parts by mass of white 833 白 and 1.5 parts by mass of silane X50S was added, and the mixture was kneaded for 40 seconds, and the top plug was cleaned and kneaded for 0 seconds. Discharge; the pressurization mixing time is 210 seconds, and the discharge temperature is 210 degrees Celsius.
二段混炼工艺：  Two-stage mixing process:
在车 90r/min的密炼机中力口入 90质量份炭黑母胶，以及 65质量份白炭黑母胶， 混炼 60秒 顶栓加入 3质量份氧化锌、 2质量份硬脂酸、 1.5质量份防老剂 RD、 2 质量份防老剂 020、 1质量份防护蜡， 混炼 80秒清扫， 在混炼 30秒排出二段母胶， 加 215 压混炼时间为 170秒， 排胶 ¾¾t为 154°C。  In the 90r/min mixer, 90 parts by mass of carbon black masterbatch and 65 parts by mass of silica black masterbatch were mixed, and 60 seconds of top plug was added to add 3 parts by mass of zinc oxide and 2 parts by mass of stearic acid. 1.5 parts by mass of anti-aging agent RD, 2 parts by mass of anti-aging agent 020, 1 part by mass of protective wax, mixing for 80 seconds, mixing two-stage masterbatch in mixing for 30 seconds, adding 215 pressing time for 170 seconds, discharging glue 3⁄43⁄4t is 154 °C.
终炼胶混炼工艺：  Final rubber mixing process:
在转速为 50r/min的密炼机中力口入 164.5质量份二段母胶，混炼 30秒后 f^i:顶栓加 入 1质量份硫黄， 1.5质量份 ί腿剂 CZ,， 混炼 60秒清扫， 在混炼 30秒排除终炼胶， 加压混炼时间为 120秒， 排胶 ¾¾t为 102°C。  In the internal mixer with a rotational speed of 50r/min, 164.5 parts by mass of the second-stage masterbatch was injected into the mouth, and after 30 seconds of mixing, f^i: the top plug was added with 1 part by mass of sulfur, 1.5 parts by mass of the legged agent CZ, and kneaded. After 60 seconds of cleaning, the final rubber was removed after mixing for 30 seconds. The pressure mixing time was 120 seconds, and the rubber discharge was 3⁄43⁄4t at 102 °C.
220 表 5: 实施例 3和对比例 3的性倉^ (寸比 对比例 3 实施例 3 220 Table 5: Sexual warehouses of Example 3 and Comparative Example 3 Comparative Example 3 Example 3
硬度（ShoreA度） 65 64 拉伸强度 (MPa) 28.4 29.3 扯断伸长率 (％) 460 473  Hardness (ShoreA degree) 65 64 Tensile strength (MPa) 28.4 29.3 Elongation at break (%) 460 473
物理性能  Physical properties
撕裂强度 (N/匪） 122 114 室温弹性(％) 56 59  Tear strength (N/匪) 122 114 Room temperature elasticity (%) 56 59
60°C弹性 (%) 65 68 底部温升 (°c) 21.1 19.5 60°C elasticity (%) 65 68 bottom temperature rise (°c) 21.1 19.5
25min压缩生热  25min compression heat generation
永久形变 (％) 1.2 1.1 阿克隆磨耗体积 (cm3) 0.26 0.23 Permanent deformation (%) 1.2 1.1 Acron wear volume (cm 3 ) 0.26 0.23
磨耗性能  Wear performance
DIN磨耗体积 (cm3) 0.175 0.154 实施例 3与对比例 3相比， 弹性提高， 压缩生热降低， 磨耗性能提高， 说明当采 用本发明混炼工艺， 生热降低， 弹性提高， 耐磨性提高。 DIN abrasion volume (cm 3 ) 0.175 0.154 Compared with Comparative Example 3, Example 3 has improved elasticity, reduced heat generation and improved wear performance, indicating that when the mixing process of the present invention is employed, heat generation is reduced, elasticity is improved, and abrasion resistance is improved. improve.

Claims

权 利 要 求 书 12 Claim 12
1、一种含天然橡 J¾/炭黑和合成聚异戊二烯橡臉白炭黑母胶的橡胶组合物及制备工 艺， 其特征在于： 1. A rubber composition containing natural rubber/carbon black and synthetic polyisoprene rubber/white carbon black masterbatch and its preparation process, which is characterized by:
母炼胶工艺： Masterbatch process:
炭黑母胶工艺： 天然胶与炭黑在密炼机中混炼生成炭黑母胶； Carbon black masterbatch process: Natural rubber and carbon black are mixed in an internal mixer to form carbon black masterbatch;
白炭黑母胶工艺： 合成聚异戊二烯橡胶与白炭黑、 偶联剂在密炼机中混炼生成白 炭黑母胶； Silica masterbatch process: Synthetic polyisoprene rubber, silica, and coupling agent are mixed in an internal mixer to form silica masterbatch;
终炼胶工艺： Final rubber mixing process:
将所述炭黑母胶、 白炭黑母胶、 防老剂、 活性剂、 促进剂、 硫化剂按组合物比例 混炼制备成橡胶组合物。 The carbon black masterbatch, silica masterbatch, antioxidant, activator, accelerator, and vulcanizing agent are mixed according to the composition ratio to prepare a rubber composition.
2、 根据权利要求 1所述的制备方法， 以橡胶总用量 100质量份计， 天然橡胶与合成 聚异戊二烯橡胶的用量比为 1:3— 5:1;炭黑 /白炭黑用量比例与天然臉合成聚异戊二烯橡 胶的用量比例保持一定比例，一般使两种填料的比例与两种橡胶比例保持一致；炭黑与 白炭黑的总用量为 5-120质量份， 优选 10-100质量份； 2. The preparation method according to claim 1, based on 100 parts by mass of the total amount of rubber, the amount ratio of natural rubber to synthetic polyisoprene rubber is 1:3-5:1; the amount of carbon black/silica black The ratio should be kept at a certain ratio with the amount of natural synthetic polyisoprene rubber. Generally, the ratio of the two fillers should be consistent with the ratio of the two rubbers; the total amount of carbon black and silica should be 5-120 parts by mass, preferably 10-100 parts by mass;
3、 †艮据权利要求 1所述的制备方法， 炭黑母胶以天然橡胶 100质量份计， 炭黑用量 为 5-100份，优选 20-80份； 白炭黑母胶以合成聚异戊二烯橡胶 100质量份计， 白炭黑用量 为 5-100份， 优¾-80份， 偶联剂用量为白炭黑的 0.5wt%-20wt%优选 lwt%— 15wt%; 3. According to the preparation method of claim 1, the carbon black masterbatch is based on 100 parts by mass of natural rubber, and the amount of carbon black is 5-100 parts, preferably 20-80 parts; the white carbon black masterbatch is synthetic polyisotope. Based on 100 parts by mass of pentadiene rubber, the amount of silica used is 5-100 parts, preferably ¾-80 parts, and the amount of coupling agent is 0.5wt%-20wt% of silica, preferably 1wt%-15wt% ;
4、根据权利要求 1舰的制备方法， 天然橡胶包括标准胶、杜仲胶、烟片胶、银菊 胶；其中合成聚异戊二烯t胶为顺式聚异戊二烯t胶、反式聚异戊二烯橡胶或它们的混 合物。 4. The preparation method according to claim 1, the natural rubber includes standard rubber, Eucommia gum, tobacco rubber, and guayule rubber; wherein the synthetic polyisoprene T rubber is cis polyisoprene T rubber, trans polyisoprene T rubber. Polyisoprene rubber or mixtures thereof.
5、 根据权利要求 1所述的制备方法， 其中所述炭黑为任意炭黑， 优选 STSA比表面 积¾70-180111 ， 压 ft)BP吸收值为 60-150(10— 5m3/kg) 的炭黑； 所述白炭黑为任意白炭 黑， 优选沉淀法白炭黑， 比表面积为 50-200m2/g。 5. The preparation method according to claim 1, wherein the carbon black is any carbon black, preferably one with an STSA specific surface area of ¾70-180111 and a BP absorption value of 60-150 ( 10-5 m3 /kg) Carbon black; The white carbon black is any white carbon black, preferably precipitation method white carbon black, with a specific surface area of 50-200 m 2 /g.
6、 根据权利要求 1所述的制备方法， 其中所述偶联剂包括最常用的双（三乙氧基 丙基硅烷）四硫化物和二硫化物、 3-硫氰基丙基-三乙氧基硅烷、 γ -蔬基-三甲氧基硅烷、 锆酸酯偶联剂、酞酸酯偶联剂、硝基偶联剂、醇类化合物， 戶; Μ醇类化合物包括但不限 于丙醇、 丁醇、 乙二醇、 聚乙二醇及其衍生物。 6. The preparation method according to claim 1, wherein the coupling agent includes the most commonly used bis(triethoxy Propylsilane) tetrasulfide and disulfide, 3-thiocyanatopropyl-triethoxysilane, γ-vegetable-trimethoxysilane, zirconate coupling agent, phthalate coupling agent, Nitro coupling agents, alcohol compounds, M alcohol compounds include but are not limited to propanol, butanol, ethylene glycol, polyethylene glycol and their derivatives.
7、†艮据权利要求 1戶; ¾，其中活化剂为金属氧化物和脂肪酸组合以及脂肪酸金属皂 盐一种或多种， 金属氧化物为氧化锌、氧化镁等一种或多种， 所述脂肪酸金属皂盐 为硬脂酸锌、 硼酸锌等一种或多种。 7. According to claim 1; ¾, wherein the activator is one or more combinations of metal oxides and fatty acids and fatty acid metal soap salts, and the metal oxide is one or more zinc oxide, magnesium oxide, etc., so The fatty acid metal soap salt is one or more of zinc stearate, zinc borate, etc.
8、 根据权利要求 1所述的制备方法， 其中防老剂包括胺类防老剂、 喹啉类防老剂、 苯并咪唑类防老剂、 防护蜡一种或多种。 8. The preparation method according to claim 1, wherein the antioxidant includes one or more types of amine antioxidants, quinoline antioxidants, benzimidazole antioxidants, and protective waxes.
9、根据权利要求 1戶; M的橡胶组合物，其中促进剂包括但不限于次磺酰胺类 ί腿剂 9. The rubber composition according to claim 1, wherein the accelerator includes but is not limited to sulfenamide accelerators
、 噻唑类促进剂、禾烂姆类碰剂、胍类促进剂或它们的组合， 硫化剂包括但不限于硫 黄、 不溶性硫黄、 充油硫黄、 硫黄给予体或它们的组合。 , thiazole accelerators, gram accelerators, guanidine accelerators or their combinations, vulcanizing agents include but are not limited to sulfur, insoluble sulfur, oil-extended sulfur, sulfur donors or their combinations.
10、 一种†艮据权利要求 1-9戶; M制备方法制备的混炼胶或 化胶。 10. A mixed rubber or rubber prepared according to the preparation method of claims 1-9.
PCT/CN2014/082701 2014-01-23 2014-07-22 Rubber composition with natural rubber/carbon black and synthetic polyisoprene rubber/white carbon black as master batch and manufacturing process therefor WO2015109791A1 (en)

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