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CN108003408B - Vulcanized rubber and preparation method and application thereof - Google Patents

Vulcanized rubber and preparation method and application thereof Download PDF

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Publication number
CN108003408B
CN108003408B CN201610934758.1A CN201610934758A CN108003408B CN 108003408 B CN108003408 B CN 108003408B CN 201610934758 A CN201610934758 A CN 201610934758A CN 108003408 B CN108003408 B CN 108003408B
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rubber
mixing
carbon black
white carbon
temperature
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CN108003408A (en
Inventor
王丽静
解希铭
唐功庆
陈婧
郑方远
王雷雷
姜科
王丽丽
李静
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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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
    • 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
    • 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
    • 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
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • 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
    • 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
    • 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

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The invention relates to the field of rubber processing application, and discloses vulcanized rubber as well as a preparation method and application thereof, wherein the method comprises the following steps: (1) carrying out first mixing on a part of white carbon black composition and a part of main rubber or softener; secondly, performing second mixing on the first mixed rubber obtained after the first mixing and the residual white carbon black composition to obtain second mixed rubber; (2) carrying out third mixing on the residual main rubber and the second mixed rubber to obtain third mixed rubber; (3) carrying out fourth mixing on the third mixed rubber, carbon black and an anti-aging agent or a softening agent and/or the rest of activating agent to obtain a fourth mixed rubber; then, carrying out fifth mixing on the fourth mixed rubber, a vulcanizing agent and a vulcanization accelerator to obtain fifth mixed rubber; (4) and vulcanizing the fifth rubber compound. The invention can obtain vulcanized rubber with excellent mechanical properties, low heat generation, low rolling resistance, good wet skid resistance and excellent wear resistance.

Description

Vulcanized rubber and preparation method and application thereof
Technical Field
The invention relates to the field of rubber processing application, in particular to a method for preparing vulcanized rubber, the vulcanized rubber prepared by the method and application of the vulcanized rubber in preparing tires.
Background
Along with the aggravation of the world energy crisis and environmental pollution, energy conservation and environmental protection are more and more emphasized in various countries. The automotive industry is also moving towards energy conservation and environmental protection in order to reduce fuel consumption and greenhouse gas emissions.
In 2009, two new regulations relating to tires were promulgated by the european union, and there was a demand for maximum improvement in tire safety, reduction in fuel consumption, and reduction in noise. This puts higher demands on the performance of the tire, and requires that the tire has good grip on the road surface on the premise of ensuring a high driving range (wear resistance of the tread), particularly good wet skid resistance on wet and slippery road surfaces in rainy days and on icy and snowy road surfaces. High performance tires, on the other hand, require low rolling resistance, good wet skid resistance and excellent wear resistance.
At the end of the 20 th century, Michelin proposed a concept of 'green tires', and means that white carbon black is used as a reinforcing agent to replace carbon black in a tire tread rubber formula, so that rolling resistance of the tires is reduced, oil consumption is reduced, and the aims of reducing automobile emission, saving energy and reducing emission are fulfilled.
The rubber industry (2012,2:84-90) contrasts and studies that carbon black and white carbon black with the same volume fraction are adopted to respectively reinforce the performances of solution-polymerized styrene-butadiene rubber and emulsion-polymerized styrene-butadiene rubber tread rubber. The results show that: compared with the carbon black filled styrene-butadiene rubber material, the dispersibility of the carbon black filled material subjected to heat treatment by the coupling agent Si69 is improved, the 300% stress at definite elongation of vulcanized rubber is increased, the elongation at break is reduced, the wet-skid resistance is improved, the rolling resistance and dynamic heat generation are reduced, and the wear resistance and the cutting resistance are poorer.
The tire industry (2007,1:25-30) discusses the influence of the white carbon black/carbon black blending ratio on the performances of the rubber of the tire tread of the emulsion styrene-butadiene rubber ESBR1721 and the solution styrene-butadiene rubber SSBR Y837V2 passenger cars. The results show that, as the white carbon black/carbon black blending ratio increases, the tan value and the rolling loss at 60 ℃ of the ESBR1721 and SSBR Y837V2 vulcanized rubber linearly decrease, the tan value and the lateral factor at 0 ℃ linearly increase, and the wear resistance slightly decreases.
In the production of green tires, a large amount of high-structure white carbon black is used in the formula, the white carbon black is not easy to disperse during mixing, the hardness of rubber materials can be improved during large amount of mixing, and heat generation during mixing is large, so that the process implementation and processing difficulty in the production process of tires is high.
Therefore, it is necessary to develop a new processing technique to obtain a vulcanized rubber having excellent mechanical properties, low heat generation, low rolling resistance, good wet skid resistance and excellent wear resistance.
Disclosure of Invention
The invention aims to provide a novel method for preparing vulcanized rubber, so as to obtain the vulcanized rubber with excellent mechanical properties, low heat generation, low rolling resistance, good wet skid resistance and excellent wear resistance.
In order to achieve the above object, the present invention provides, in a first aspect, a method for producing a vulcanized rubber, the method comprising:
(1) performing first mixing on a part of the white carbon black composition and a part of the main rubber optionally together with a softener; secondly, performing second mixing on the first mixed rubber obtained after the first mixing and the rest of the white carbon black composition to obtain a second mixed rubber, wherein the white carbon black composition is obtained by premixing white carbon black, a coupling agent and at least part of an activating agent;
(2) performing third mixing on the rest part of the main rubber and the second mixed rubber to obtain third mixed rubber;
(3) performing fourth mixing on the third mixed rubber, carbon black and an anti-aging agent, and optionally a softening agent and/or the rest of an activating agent to obtain a fourth mixed rubber; then, carrying out fifth mixing on the fourth mixed rubber, a vulcanizing agent and a vulcanization accelerator to obtain fifth mixed rubber;
(4) and vulcanizing the fifth rubber compound.
In a second aspect, the present invention provides a vulcanizate prepared by the foregoing method.
In a third aspect, the present invention provides a vulcanized rubber as described in the first aspect.
In a fourth aspect, the present invention provides the use of the aforementioned vulcanized rubber in the manufacture of a tire.
The invention provides a novel process for preparing vulcanized rubber, and the vulcanized rubber with excellent mechanical properties, low heat generation, low rolling resistance, good wet skid resistance and excellent wear resistance can be obtained.
In addition, compared with the vulcanized rubber obtained by the method for preparing the vulcanized rubber in the prior art, the vulcanized rubber obtained by the method for preparing the vulcanized rubber provided by the invention has better comprehensive physical and mechanical properties and dynamic mechanical properties.
Furthermore, the method for preparing vulcanized rubber provided by the invention also has the advantages of simple process and low cost.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
First aspectThe present invention provides a process for preparing a vulcanized rubber, the process comprising:
(1) performing first mixing on a part of the white carbon black composition and a part of the main rubber optionally together with a softener; secondly, performing second mixing on the first mixed rubber obtained after the first mixing and the rest of the white carbon black composition to obtain a second mixed rubber, wherein the white carbon black composition is obtained by premixing white carbon black, a coupling agent and at least part of an activating agent;
(2) performing third mixing on the rest part of the main rubber and the second mixed rubber to obtain third mixed rubber;
(3) performing fourth mixing on the third mixed rubber, carbon black and an anti-aging agent, and optionally a softening agent and/or the rest of an activating agent to obtain a fourth mixed rubber; then, carrying out fifth mixing on the fourth mixed rubber, a vulcanizing agent and a vulcanization accelerator to obtain fifth mixed rubber;
(4) and vulcanizing the fifth rubber compound.
The "part of the white carbon black composition" and the "the rest of the white carbon black composition" constitute the whole white carbon black composition of the invention.
The "a part of the body rubber" and the "the remaining part of the body rubber" constitute the entire body rubber of the present invention.
In the step (1), "optionally with a softener" means that the softener may or may not be added in the step (1). One skilled in the art can determine whether a softener should be added based on whether or not the main rubber is oil-extended, and the number of oil extensions.
In the step (3), "fourth mixing the third rubber compound with carbon black and an antioxidant optionally together with a softener and/or the remaining part of an activator" means that the substance participating in the fourth mixing may be the third rubber compound, carbon black and an antioxidant; or the substances participating in the fourth mixing can be the third mixing rubber, carbon black, an anti-aging agent and a softening agent; or the substances participating in the fourth mixing can be the third mixing rubber, carbon black, an anti-aging agent and the rest of the activating agent; alternatively, the substances participating in the fourth mixing may be the third mixing, carbon black, an anti-aging agent, a softener, and the remaining part of an activator. When the amount of the softener used in the step before the step (3) is insufficient, an appropriate amount of the softener may be further added in the step (3), or the softener involved in the method of the present invention may be added not at all, at one time in the step (1), at one time in the step (3), or in batches in the step (1) and the step (3). And the optional remaining part of the activator means that when the activator in the white carbon black composition of the step (1) is only a part of the total activator, the remaining part of the activator is added in the step (3).
The vulcanized rubber prepared by the method provided by the invention has excellent wet skid resistance, low rolling resistance, low compression temperature rise, small abrasion and other excellent performances and good comprehensive physical and mechanical properties.
Preferably, the portion of the white carbon composition is from 2/10 to 9/10 by weight of the total white carbon composition; more preferably, the portion of the white carbon composition is from 1/2 to 3/4 by weight of the total white carbon composition; the inventors of the present invention have found that when the weight of the first white carbon black composition is controlled to be 2/10 to 9/10, preferably 1/2 to 3/4, based on the weight of the entire white carbon black composition, the vulcanized rubber obtained by the method of the present invention has better dynamic mechanical properties.
Preferably, the portion of the body rubber is 1/12 to 1/2 of the total body rubber weight; more preferably, the portion of the body rubber is 1/4 to 1/3 of the total body rubber weight; the inventors of the present invention have found that the vulcanized rubber obtained by the method of the present invention has better dynamic mechanical properties when the weight of the first-added main rubber is controlled to be 1/12 to 1/2, preferably 1/4 to 1/3, based on the weight of the entire main rubber.
Preferably, in step (1), the conditions of the first mixing and the second mixing are the same or different, and each independently comprises: the temperature is 70-150 deg.C, and the time is 1-8 min. More preferably, the temperature of the first mixing is 70-150 ℃ and the time is 2-4 min; the temperature of the second mixing is 70-150 ℃, and the time is 2-4 min.
Preferably, in step (2), the conditions of the third mixing include: the temperature is 70-150 deg.C, and the time is 1-8 min. More preferably, the third mixing conditions include: the temperature is 70-150 deg.C, and the time is 2-4 min.
In the present invention, the temperature in the first, second and third mixing processes may be changed with the change of the mixing time, as long as the temperature in the first, second and third mixing can be controlled within the range defined in the present invention.
Preferably, in step (3), the conditions of the fourth mixing include: the temperature is 150 ℃ and 170 ℃, and the time is 4-10 min; more preferably, the fourth mixing conditions include: the temperature is 150 ℃ and 170 ℃, and the time is 5-7 min.
Preferably, in step (3), the conditions of the fifth mixing include: the temperature is 40-110 deg.C, and the time is 1-7 min; more preferably, the fifth mixing conditions include: the temperature is 40-110 deg.C, and the time is 3-5 min.
Generally, the methods and conditions for vulcanizing the fifth mix in accordance with the present invention are well known to those skilled in the art. For example, the vulcanization may be carried out in a vulcanization bed or a press; the vulcanization conditions generally include a vulcanization temperature, a vulcanization pressure and a vulcanization time, wherein the vulcanization temperature, the vulcanization pressure and the vulcanization time are only required to ensure that the crosslinking reaction of the main rubber and the vulcanizing agent can be carried out, for example, the vulcanization temperature can be 150-170 ℃, the vulcanization pressure can be 10-15MPa, and the vulcanization time can be 10-50 minutes.
Preferably, in step (1), the conditions for premixing the white carbon black, the coupling agent and at least part of the activating agent comprise: the temperature is 5-100 deg.C, and the time is 5-10 min.
Further, the method of the invention can also comprise the step of heating the premixed white carbon black composition for 0.5 to 5 hours at the temperature of between 80 and 150 ℃ before using the white carbon black composition.
And, the method of the present invention may further comprise heating the carbon black at 80 to 150 ℃ for 0.5 to 5 hours before using the carbon black.
Preferably, the method of the present invention further comprises: in the step (1) and the step (3), before the main rubber is used, the main rubber is plasticated at an initial temperature of 75-85 ℃ for 0.4-0.6 min.
Preferably, the white carbon black is used in an amount of 55-65 parts by weight, the carbon black is used in an amount of 5-15 parts by weight, the softener is used in an amount of 0-25 parts by weight, the coupling agent is used in an amount of 4-8 parts by weight, the antioxidant is used in an amount of 3-11 parts by weight, the vulcanizing agent is used in an amount of 0.5-2 parts by weight, the vulcanization accelerator is used in an amount of 2-5 parts by weight, and the activator is used in an amount of 4-8 parts by weight, relative to 100 parts by weight of the main rubber. When the main body rubber is oil-extended rubber and the content of the extended oil in the oil-extended rubber is sufficiently large, the amount of the softener to be used may be 0. In the present invention, the optional kind of the softening agent is the same as the optional kind of the extender oil.
In the present invention, unless otherwise specified, 100 parts by weight of the main body rubber in "with respect to 100 parts by weight of the main body rubber" is not included in parts by weight of the extender oil which may be contained therein. That is, when the main rubber contains the extender oil, the content of the extender oil is not included with the oil-extended main rubber as a reference. The person skilled in the art should not be construed as limiting the invention.
Preferably, the main rubber is styrene butadiene rubber. More preferably, the styrene-butadiene rubber is solution-polymerized styrene-butadiene rubber and/or emulsion-polymerized styrene-butadiene rubber.
Particularly preferably, the styrene-butadiene rubber is selected from at least one of oil-extended solution-polymerized styrene-butadiene rubber, non-oil-extended solution-polymerized styrene-butadiene rubber, and emulsion-polymerized styrene-butadiene rubber.
When the styrene-butadiene rubber is a non-oil-extended solution-polymerized styrene-butadiene rubber, a softening agent may be used in step (1) and/or step (3) of the present invention.
Preferably, the oil-extended solution-polymerized styrene-butadiene rubber has a bound styrene content of 23 to 28 wt%; a vinyl content of 55 to 66 wt.%; mooney viscosity of 55-67; the oil extended parts are 15-37.5 phr.
Preferably, the non-oil-extended solution-polymerized styrene-butadiene rubber has a bound styrene content of 20 to 30 wt%; the vinyl content is 50-60 wt%; the Mooney viscosity is 60-68.
Preferably, the emulsion polymerized styrene-butadiene rubber has a bound styrene content of 22 to 25 wt%; mooney viscosity of 45-60; the oil extended fraction is 0-50 phr.
Preferably, the carbon black has an iodine absorption value of not less than 80g/kg, an average particle diameter of 10 to 40 nm and a specific surface area of 80 to 140m2/g。
Preferably, the specific surface area of the white carbon black is 100-200m2(ii)/g, more preferably 115-200m2/g。
Preferably, the softening agent is a petroleum-based softening agent, more preferably an aromatic oil and/or a naphthenic oil. For example, the softening agent may be at least one of TDAE (Treated Aromatic oil), RAE (Residual Aromatic Extract), and NAP (naphthenic oil). In the present invention, the properties of the aromatic oil and the naphthenic oil are not particularly limited, and may be various aromatic oils and naphthenic oils as generally used in the art.
Preferably, the coupling agent is a silane coupling agent, more preferably, the coupling agent is at least one of Si69 (bis- [ γ - (triethoxysilyl) propyl ] -tetrasulfide), KH550(γ -aminopropyltriethoxysilane), and Si75 (bis- [ γ - (triethoxysilyl) propyl ] -disulfide).
Preferably, the antioxidant is selected from at least one of microcrystalline wax, amine antioxidant and quinoline antioxidant. More preferably, the antioxidant is a mixture of microcrystalline wax and at least one selected from the group consisting of 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer (antioxidant RD), 2-mercaptobenzimidazole (antioxidant MB), and N-cyclohexyl-N' -phenyl-p-phenylenediamine (antioxidant 4010).
When the antioxidant is a mixture of microcrystalline wax and at least one substance selected from the group consisting of antioxidant RD, antioxidant MB and antioxidant 4010, it is preferable that the content ratio by weight of the microcrystalline wax to the at least one substance selected from the group consisting of antioxidant RD, antioxidant MB and antioxidant 4010 is 1: 1.2-3.
Preferably, the vulcanizing agent is sulfur.
Preferably, the vulcanization accelerator is at least one of diphenylguanidine (accelerator DPG), N-tert-butyl-2-benzothiazylsulfenamide (accelerator TBBS), 2' -dibenzothiazyl disulfide, N-tert-butyl-bis (2-benzothiazole) sulfenimide, and N-cyclohexyl-bis (2-mercaptobenzothiazole) sulfenamide.
Preferably, the activator is at least one of zinc oxide, magnesium oxide and stearic acid.
According to a preferred embodiment, the process for preparing a vulcanized rubber of the present invention comprises:
1. premixing white carbon black, a coupling agent and at least part of an activating agent for 5-10min at 5-100 ℃ to obtain a white carbon black composition, and heating the white carbon black composition for 0.5-5h at 80-150 ℃ before use; and before use, heating the carbon black for 0.5-5h at the temperature of 80-150 ℃;
2. performing first mixing on a part of the white carbon black composition and a part of the main rubber optionally together with a softener; secondly, performing second mixing on the first mixed rubber obtained after the first mixing and the rest of the white carbon black composition to obtain second mixed rubber; wherein a portion of the white carbon black composition accounts for 1/2-3/4 of the total weight of the white carbon black composition, and a portion of the main body rubber accounts for 1/4-1/3 of the total weight of the main body rubber; the conditions of the first mixing and the second mixing are the same or different, and each independently include: the temperature is 70-150 deg.C, and the time is 1-8 min;
3. performing third mixing on the rest part of the main rubber and the second mixed rubber to obtain third mixed rubber; the conditions of the third mixing include: the temperature is 70-150 deg.C, and the time is 1-8 min;
4. performing fourth mixing on the third mixed rubber, carbon black and an anti-aging agent, and optionally a softening agent and the rest of activating agent to obtain a fourth mixed rubber; then, carrying out fifth mixing on the fourth mixed rubber, a vulcanizing agent and a vulcanization accelerator to obtain fifth mixed rubber; wherein the fourth mixing conditions include: the temperature is 150 ℃ and 170 ℃, and the time is 4-10 min; the fifth mixing conditions include: the temperature is 40-110 deg.C, and the time is 1-7 min;
5. vulcanizing the fifth rubber compound; the conditions of the vulcanization reaction comprise that the vulcanization temperature is 150-170 ℃, the vulcanization pressure is 10-15MPa, and the vulcanization time is 10-50 minutes; and
in the step (1) and the step (3), before the main rubber is used, the main rubber is plasticated at 75-85 ℃ for 0.4-0.6 min.
According to a more preferred embodiment of the present invention, the method for preparing a vulcanized rubber of the present invention comprises:
1. premixing white carbon black, a coupling agent and at least part of an activating agent for 5-10min at 5-100 ℃ to obtain a white carbon black composition, and heating the white carbon black composition for 0.5-5h at 80-150 ℃ before use; and before use, heating the carbon black for 0.5-5h at the temperature of 80-150 ℃;
2. adding a part of main rubber into an internal mixer for plastication for 0.4-0.6min, wherein the rotating speed of the internal mixer is 85-95rpm, and the initial internal mixing temperature is 75-85 ℃;
3. adding a part of white carbon black composition and all softening agents into an internal mixer, and carrying out first mixing for 2-4min at 70-150 ℃ to obtain a first mixed rubber; then adding the rest white carbon black composition into an internal mixer, and carrying out second mixing for 2-4min at the temperature of 70-150 ℃; unloading the rubber material, and rolling and cutting the rubber material into pieces on a double-roller open mill to obtain a second rubber compound;
4. adding the rest of main rubber into an internal mixer for plastication for 0.4-0.6min, wherein the rotating speed of the internal mixer is 85-95rpm, and the initial internal mixing temperature is 75-85 ℃; then adding the second mixed rubber into an internal mixer for third mixing at 70-150 ℃ for 1-8min to obtain third mixed rubber;
5. adding the carbon black, the anti-aging agent and the rest activating agent into an internal mixer for fourth mixing, and unloading the obtained fourth mixed rubber when the internal mixing temperature reaches 150-170 ℃ and is kept for 4-10 min;
6. passing the fourth rubber compound on an open mill with the roller spacing of 4-6mm and the roller temperature of 50 +/-5 ℃ for three times; standing for 3.5-4.5h by using a mixing adhesive;
7. adjusting the rotation speed of an internal mixer to 55-65rpm, adjusting the temperature to 40 +/-5 ℃, adding the mixed rubber obtained in the step 6 into the internal mixer, mixing for 20-60s, adding a vulcanizing agent and a vulcanization accelerator for fifth mixing, and unloading the obtained fifth mixed rubber when the temperature of the rubber material reaches 110-120 ℃ and the temperature is kept for 1-7 min;
8. passing the fifth rubber compound once on an open mill with the roller spacing of 0.4-0.6mm and the roller temperature of 50 +/-5 ℃, adjusting the roller spacing to 2-4mm, and passing twice; standing the mixed rubber for 20-28 h;
9. and (3) vulcanizing the rubber material obtained in the step (8), wherein the vulcanization conditions comprise: the vulcanization temperature is 150-c90And (4) determining.
Second aspect of the inventionThe invention provides a vulcanized rubber prepared by the method.
Third aspect of the inventionThe present invention provides the vulcanized rubber described in the first aspect.
In the third aspect of the present invention, the vulcanized rubber means a vulcanized rubber having the properties of the vulcanized rubber produced by the method of the first aspect of the present invention, and is not necessarily produced by the method of the first aspect of the present invention as defined in the second aspect of the present invention. That is, the method for producing the vulcanized rubber of the third aspect of the present invention is not limited as long as a product having the same properties as the vulcanized rubber of the first aspect can be obtained.
Fourth aspect of the inventionThe invention provides the use of the aforementioned vulcanized rubber in the manufacture of tires.
The present invention will be described in detail below by way of examples.
The properties of the vulcanizates of this invention were tested as follows:
mechanical properties: and (3) adopting a material testing machine (SHIMADZU, AG-20KNG) to carry out the test characterization of the mechanical property of the prepared material. The force sensor selected by the material testing machine is 1 KN. According to the national standard GB/T528-2009, the stretching rate is 500mm/min, and the test temperature is 23 +/-2 ℃. The effective portion of the sample had a length of 25mm and a width of 6 mm. For each set of samples, 5 replicates were run and the results averaged.
Dynamic mechanical properties: temperature scanning was carried out on a dynamic thermomechanical analyzer eplex 500N, GABO, germany, using a tensile fixture, with a test frequency of 11Hz and a temperature range: the temperature is from 80 ℃ below zero to 80 ℃ above zero, the heating rate is 3 ℃/min, the static strain is 1 percent, and the dynamic strain is 0.25 percent.
Dynamic compression fatigue heat generation: the samples were tested for dynamic compression fatigue heat generation according to GB/T1687 + 1993 using a RH-2000 type rubber compression heat generation tester manufactured by Beijing Youth deep electronics Co. And (3) testing conditions are as follows: the stroke is 4.45mm, the load is 1MPa, the temperature is 55 ℃, and the time is 25 min.
DIN abrasion: according to the regulations in GB/T9867-.
Resilience performance: the rebound resilience is measured by adopting a GT-7042-RE type rubber elasticity testing machine of Taiwan high-speed railway company in accordance with the national standard GB/T1681-2009 vulcanized rubber rebound resilience measurement.
Vulcanization characteristics of the rubber compound: measured by a rotor-free vulcanizer according to the GB/T16584-1996 standard, and the test temperature is 160 ℃.
In the invention, the specific surface area is measured by a BET specific surface area method.
The following material sources were used:
styrene-butadiene rubber (SBR) is a commercial product of SSBR2636 and SSBR2506 available from yanshan division of petrochemical gmbh, china, wherein SSBR2636 (oil-extended solution-polymerized styrene-butadiene rubber) has a bound styrene content of 25 wt%, a vinyl content of 63 wt%, a mooney viscosity of 62, and an oil-extended part of 37.5 phr; SSBR2506 (a non oil-extended solution-polymerized styrene-butadiene rubber) has 26% by weight of bound styrene, a vinyl content of 56% by weight, a Mooney viscosity of 65 and an oil-extended fraction of 0 phr.
The carbon black is purchased from Tianjin Yibo Rui chemical Co Ltd and has the brand number of N115 (the iodine absorption value is 160g/kg, the specific surface area is 137 m)2(g), N234 (iodine absorption value of 120g/kg, specific surface area of 119 m)2(g), N330 (iodine absorption value of 82g/kg, specific surface area of 78 m)2Commercial product of/g).
The white carbon black is a commodity of high-dispersity granular white carbon black with the mark of 165GR and high-specific-surface microbead white carbon black with the mark of 1165MP which are purchased from Solvay fine chemical additives (Qingdao) Limited company, and the specific surface areas of the high-dispersity granular white carbon black and the high-specific-surface microbead white carbon black are both 165m2/g。
Sulfur (vulcanizing agent) is a commercial product available from Chemicals, Inc., national drug group.
Accelerator D (vulcanization accelerator) is a commercial product from morning chemical ltd, shijiazhuan.
The accelerator TBBS (vulcanization accelerator) is a commercial product from the new materials science ltd, guangdong.
ZnO (activator) is a commercial product available from the national pharmaceutical group chemical agents Co.
SA (stearic acid) (activator) is a commercial product available from the pharmaceutical group chemicals limited.
The microcrystalline wax is a commodity which is purchased from Tianjin Hengshengxin international trade company Limited and has the brand number of W-445, and the number of carbon atoms is 20-50.
Si69 and Si75 (silane coupling agents) are commercial products from chemical technology, Inc., Shanghai Rui.
2,2, 4-trimethyl-1, 2-dihydroquinoline polymer (antioxidant RD) and 2-mercaptobenzimidazole (antioxidant MB) are commercial products available from Shanghai Kangjin chemical Co., Ltd.
N-cyclohexyl-N' -phenyl-p-phenylenediamine (antioxidant 4010) is a commercial product available from Ginko city Li and chemical Co., Ltd.
The softener is an environment-friendly aromatic oil TDAE purchased from Zibo Qian shun plastics Limited company, and the aromatic hydrocarbon content is more than or equal to 85 percent.
The components for producing a vulcanized rubber referred to in the following examples were the same in total amount and 1200g each.
Example 1: method for preparing vulcanized rubber S1
The formulation of each component involved in the process of this example is shown in table 1 (where the numerical values are parts by weight obtained with respect to 100 parts by weight of the main rubber). The preparation method of the vulcanized rubber S1 of the embodiment is specifically as follows:
1. mixing white carbon black, a silane coupling agent and stearic acid in a high-speed mixer for 10min at 40 ℃, then grinding for 3 times and 10s each time in a high-speed grinder to obtain a white carbon black composition, and insulating the white carbon black composition in an oven at 140 ℃ for 2h before use; the carbon black is kept in a 110 ℃ oven for 2h before use;
2. adding 1/3 solution polymerized styrene-butadiene rubber accounting for the weight of all solution polymerized styrene-butadiene rubber into an internal mixer for plastication for 0.5min, wherein the rotating speed of the internal mixer is 90rpm, and the initial temperature of the plastication is 80 ℃;
3. adding the 3/4 white carbon black composition obtained in the step 1 and all softeners into an internal mixer for first mixing for 2min, wherein the weight of the white carbon black composition is 3/4, and the temperature in the internal mixer is controlled not to exceed 140 ℃; then adding the rest white carbon black composition into an internal mixer, and controlling the temperature in the internal mixer within the range of not more than 140 ℃ for second mixing for 2 min; unloading the rubber material, and rolling and cutting the rubber material into pieces on a double-roller open mill to obtain a second rubber compound;
4. adding the rest of solution polymerized styrene butadiene rubber into an internal mixer for plastication for 0.5min, wherein the rotating speed of the internal mixer is 90rpm, and the initial internal mixing temperature is 80 ℃; adding the second rubber compound into an internal mixer, and carrying out third mixing for 2min under the condition that the temperature in the internal mixer is controlled not to exceed 140 ℃ to obtain a third rubber compound;
5. adding carbon black, an anti-aging agent and zinc oxide into an internal mixer for fourth mixing, keeping the internal mixing temperature for 5min when the internal mixing temperature reaches 150 ℃, and then unloading the obtained fourth mixed rubber;
6. passing the fourth rubber compound on an open mill with the roller spacing of 5mm and the roller temperature of 50 ℃ for three times; standing for 4 hours by using a mixing adhesive;
7. adjusting the rotation speed of an internal mixer to 60rpm, controlling the temperature to 40 ℃, adding the mixed rubber obtained in the step 6 into the internal mixer, mixing for 30s, adding a vulcanizing agent and a vulcanization accelerator, performing fifth mixing, and unloading the obtained fifth mixed rubber when the temperature of the rubber reaches 110 ℃ and is kept at the temperature for 4 min;
8. passing the fifth rubber compound obtained in the step 7 once on an open mill with the roller spacing of 0.5mm and the roller temperature of 50 ℃, adjusting the roller spacing to 3mm, and passing twice; standing the mixed rubber for 24 hours;
9. vulcanizing the rubber material obtained in the step 8, wherein the vulcanization temperature is 160 ℃, the pressure is 15MPa, and the vulcanization time is determined according to the positive vulcanization time t measured by a rotor-free vulcanizing instrumentc90The determination was 30 min.
As a result, a vulcanized rubber S1 was obtained.
Example 2: method for preparing vulcanized rubber S2
The formulation of each component involved in the process of this example is shown in table 1 (where the numerical values are parts by weight obtained with respect to 100 parts by weight of the main rubber). The preparation method of the vulcanized rubber S2 of the embodiment is specifically as follows:
1. mixing white carbon black, a silane coupling agent and stearic acid in a high-speed mixer for 5min at 70 ℃, then grinding in a high-speed grinder for 5 times and 8s each time to obtain a white carbon black composition, and insulating the white carbon black composition in an oven at 120 ℃ for 3h before use; the carbon black is kept in a 110 ℃ oven for 2h before use;
2. adding 1/4 solution polymerized styrene-butadiene rubber accounting for the weight of all solution polymerized styrene-butadiene rubber into an internal mixer for plastication for 0.4min, wherein the rotating speed of the internal mixer is 90rpm, and the initial temperature of the plastication is 85 ℃;
3. adding the 1/2 white carbon black composition obtained in the step 1 and all softeners into an internal mixer for first mixing for 2min, wherein the weight of the white carbon black composition is 1/2, and the temperature in the internal mixer is controlled not to exceed 140 ℃ to obtain a first mixed rubber; then adding the rest white carbon black composition into an internal mixer, and controlling the temperature in the internal mixer within the range of not more than 140 ℃ to perform second mixing for 2 min; unloading the rubber material, and rolling and cutting the rubber material into pieces on a double-roller open mill to obtain a second rubber compound;
4. adding the rest of solution polymerized styrene butadiene rubber into an internal mixer for plastication for 0.4min, wherein the rotating speed of the internal mixer is 90rpm, and the initial temperature of internal mixing is 85 ℃; adding the second rubber compound into an internal mixer, and carrying out third mixing for 2min under the condition that the temperature in the internal mixer is controlled not to exceed 140 ℃ to obtain a third rubber compound;
5. adding carbon black, an anti-aging agent and zinc oxide into an internal mixer for fourth mixing, keeping the internal mixing temperature for 5min when the internal mixing temperature reaches 160 ℃, and then unloading the obtained fourth mixed rubber;
6. passing the fourth rubber compound on an open mill with the roller spacing of 5mm and the roller temperature of 50 ℃ for three times; standing for 4 hours by using a mixing adhesive;
7. adjusting the rotation speed of an internal mixer to 60rpm, controlling the temperature to 40 ℃, adding the mixed rubber obtained in the step 6 into the internal mixer, mixing for 30s, adding a vulcanizing agent and a vulcanization accelerator, performing fifth mixing, and unloading the obtained fifth mixed rubber when the temperature of the rubber reaches 110 ℃ and is kept at the temperature for 4 min;
8. passing the fifth rubber compound obtained in the step 7 once on an open mill with the roller spacing of 0.5mm and the roller temperature of 50 ℃, adjusting the roller spacing to 3mm, and passing twice; standing the mixed rubber for 24 hours;
9. vulcanizing the rubber material obtained in the step 8, wherein the vulcanization temperature is 150 ℃, the pressure is 14MPa, and the vulcanization time is determined according to the positive vulcanization time t measured by a rotor-free vulcanizing instrumentc90The determination was 30 min.
As a result, a vulcanized rubber S2 was obtained.
Example 3: method for preparing vulcanized rubber S3
The formulation of each component involved in the process of this example is shown in table 1 (where the numerical values are parts by weight obtained with respect to 100 parts by weight of the main rubber). The preparation method of the vulcanized rubber S3 of the embodiment is specifically as follows:
1. mixing white carbon black, a silane coupling agent and stearic acid in a high-speed mixer for 5min at 60 ℃, then grinding for 4 times and 10s each time in a high-speed grinder to obtain a white carbon black composition, and insulating the white carbon black composition in an oven at 120 ℃ for 3h before use; the carbon black is kept in an oven at 100 ℃ for 2h before use;
2. adding 7/24 solution polymerized styrene-butadiene rubber accounting for the weight of all solution polymerized styrene-butadiene rubber into an internal mixer for plastication for 0.4min, wherein the rotating speed of the internal mixer is 90rpm, and the initial temperature of the plastication is 75 ℃;
3. adding the 5/8 white carbon black composition obtained in the step 1 and all softeners into an internal mixer for first mixing for 2min, wherein the weight of the white carbon black composition is 5/8, and the temperature in the internal mixer is controlled not to exceed 140 ℃ to obtain a first mixed rubber; then adding the rest white carbon black composition into an internal mixer, and controlling the temperature in the internal mixer within the range of not more than 140 ℃ to perform second mixing for 2 min; unloading the rubber material, and rolling and cutting the rubber material into pieces on a double-roller open mill to obtain a second rubber compound;
4. adding the rest of solution polymerized styrene butadiene rubber into an internal mixer for plastication for 0.4min, wherein the rotating speed of the internal mixer is 90rpm, and the initial internal mixing temperature is 75 ℃; adding the second rubber compound into an internal mixer, and carrying out third mixing for 2min under the condition that the temperature in the internal mixer is controlled not to exceed 140 ℃ to obtain a third rubber compound;
5. adding carbon black, an anti-aging agent and zinc oxide into an internal mixer for fourth mixing, keeping the internal mixing temperature for 5min when the internal mixing temperature reaches 160 ℃, and then unloading the obtained fourth mixed rubber;
6. passing the fourth rubber compound on an open mill with the roller spacing of 5mm and the roller temperature of 50 ℃ for three times; standing for 4 hours by using a mixing adhesive;
7. adjusting the rotation speed of an internal mixer to 60rpm, controlling the temperature to 40 ℃, adding the mixed rubber obtained in the step 6 into the internal mixer, mixing for 30s, adding a vulcanizing agent and a vulcanization accelerator, performing fifth mixing, and unloading the obtained fifth mixed rubber when the temperature of the rubber reaches 110 ℃ and is kept at the temperature for 4 min;
8. passing the fifth rubber compound obtained in the step 7 once on an open mill with the roller spacing of 0.5mm and the roller temperature of 50 ℃, adjusting the roller spacing to 3mm, and passing twice; standing the mixed rubber for 24 hours;
9. vulcanizing the rubber material obtained in the step 8, wherein the vulcanization temperature is 170 ℃, the pressure is 12MPa, and the vulcanization is carried outAccording to the positive vulcanization time t measured by a rotor-free vulcanizerc90The determination was 30 min.
As a result, a vulcanized rubber S3 was obtained.
Example 4: method for preparing vulcanized rubber S4
This example was carried out in a similar manner to example 1, except that:
in this example, a portion of the main rubber added first was 1/6 based on the total weight of the entire main rubber, and the rest was the same as in example 1.
That is, the kinds and total amounts of the respective components involved in the method of this example were the same as those in example 1.
Vulcanized rubber S4 was obtained.
Example 5: method for preparing vulcanized rubber S5
This example was carried out in a similar manner to example 2, except that:
in this example, a portion of the silica composition added first accounted for 3/10 in the total weight of the silica composition, and the remainder was the same as in example 2.
That is, the kinds and total amounts of the respective components involved in the method of this example were the same as those in example 2.
Vulcanized rubber S5 was obtained.
Example 6: method for preparing vulcanized rubber S6
This example was carried out in a similar manner to example 4, except that:
in this example, a portion of the silica composition added first accounted for 3/10 in the total weight of the silica composition, and the remainder was the same as in example 4.
That is, the kinds and total amounts of the respective components involved in the method of this example were the same as those in example 4.
Vulcanized rubber S6 was obtained.
Comparative example 1: method for preparing vulcanized rubber DS1
The comparative example was conducted in a manner similar to that of example 1, except that the white carbon black composition and the main rubber in the comparative example were added in one step, specifically:
1. mixing white carbon black, a silane coupling agent and stearic acid in a high-speed mixer for 10min at 40 ℃, then grinding for 3 times and 10s each time in a high-speed grinder to obtain a white carbon black composition, and insulating the white carbon black composition in an oven at 140 ℃ for 2h before use; the carbon black is kept in a 110 ℃ oven for 2h before use;
2. adding all the solution polymerized styrene-butadiene rubber into an internal mixer for plasticating for 0.5min, wherein the rotating speed of the internal mixer is 90rpm, and the initial plasticating temperature is 80 ℃;
3. adding the white carbon black composition obtained in the step 1 and all the softening agents into an internal mixer for mixing for 2min, and controlling the temperature in the internal mixer to be not more than 140 ℃; unloading the rubber material, and rolling and cutting the rubber material into pieces on a double-roller open mill to obtain a second rubber compound;
4. adding the second rubber compound into an internal mixer and mixing for 2min at the temperature of the internal mixer not more than 140 ℃ under the conditions that the rotating speed of the internal mixer is 90rpm and the initial internal mixing temperature is 80 ℃;
5. adding carbon black, an anti-aging agent and zinc oxide into an internal mixer for mixing, keeping the internal mixing temperature at 150 ℃ for 5min, and then unloading the rubber material;
6. passing the rubber material on an open mill with the roller spacing of 5mm and the roller temperature of 50 ℃ for three times; standing for 4 hours by using a mixing adhesive;
7. adjusting the rotation speed of an internal mixer to 60rpm, controlling the temperature to 40 ℃, adding the mixed rubber obtained in the step 6 into the internal mixer, mixing for 30s, adding a vulcanizing agent and a vulcanization accelerator, mixing the rubber, and unloading the rubber when the temperature of the rubber reaches 110 ℃ and is kept at the temperature for 4 min;
8. passing the mixed rubber obtained in the step 7 on an open mill with the roller spacing of 0.5mm and the roller temperature of 50 ℃ for one time, adjusting the roller spacing to 3mm, and passing twice; standing the mixed rubber for 24 hours;
9. vulcanizing the rubber material obtained in the step 8, wherein the vulcanization temperature is 160 ℃, the pressure is 15MPa, and the vulcanization time is determined according to the positive vulcanization time t measured by a rotor-free vulcanizing instrumentc90The determination was 30 min.
As a result, a vulcanized rubber DS1 was obtained.
Comparative example 2: method for preparing vulcanized rubber DS2
The comparative example is carried out by adopting a method similar to that of example 2, except that the white carbon black composition in the comparative example is added in one step, and specifically:
1. mixing white carbon black, a silane coupling agent and stearic acid in a high-speed mixer for 5min at 70 ℃, then grinding in a high-speed grinder for 5 times and 8s each time to obtain a white carbon black composition, and insulating the white carbon black composition in an oven at 120 ℃ for 3h before use; the carbon black is kept in a 110 ℃ oven for 2h before use;
2. adding 1/4 solution polymerized styrene-butadiene rubber accounting for the weight of all solution polymerized styrene-butadiene rubber into an internal mixer for plastication for 0.4min, wherein the rotating speed of the internal mixer is 90rpm, and the initial temperature of the plastication is 85 ℃;
3. adding the white carbon black composition obtained in the step 1 and all the softening agents into an internal mixer for mixing for 2min, and controlling the temperature in the internal mixer to be not more than 140 ℃; unloading the rubber material, and rolling and cutting the rubber material into pieces on a double-roller open mill to obtain a second rubber compound;
4. adding the rest of solution polymerized styrene butadiene rubber into an internal mixer for plastication for 0.4min, wherein the rotating speed of the internal mixer is 90rpm, and the initial temperature of internal mixing is 85 ℃; adding the second rubber compound into an internal mixer and controlling the temperature in the internal mixer to be not more than 140 ℃ for mixing for 2 min;
5. adding carbon black, an anti-aging agent and zinc oxide into an internal mixer for mixing, keeping the internal mixing temperature for 5min when reaching 160 ℃, and then unloading the rubber material;
6. passing the rubber material on an open mill with the roller spacing of 5mm and the roller temperature of 50 ℃ for three times; standing for 4 hours by using a mixing adhesive;
7. adjusting the rotation speed of an internal mixer to 60rpm, controlling the temperature to 40 ℃, adding the mixed rubber obtained in the step 6 into the internal mixer, mixing for 30s, adding a vulcanizing agent and a vulcanization accelerator, mixing the rubber, and unloading the rubber when the temperature of the rubber reaches 110 ℃ and is kept at the temperature for 4 min;
8. passing the mixed rubber obtained in the step 7 on an open mill with the roller spacing of 0.5mm and the roller temperature of 50 ℃ for one time, adjusting the roller spacing to 3mm, and passing twice; standing the mixed rubber for 24 hours;
9. vulcanizing the rubber material obtained in the step 8, wherein the vulcanization temperature is 150 ℃, the pressure is 14MPa, and the vulcanization time is determined according to the positive vulcanization time t measured by a rotor-free vulcanizing instrumentc90The determination was 30 min.
As a result, a vulcanized rubber DS2 was obtained.
Comparative example 3: method for preparing vulcanized rubber DS3
This comparative example was conducted in a similar manner to example 3, except that the main rubber in this comparative example was added in one portion, specifically:
1. mixing white carbon black, a silane coupling agent and stearic acid in a high-speed mixer for 5min at 60 ℃, then grinding for 4 times and 10s each time in a high-speed grinder to obtain a white carbon black composition, and insulating the white carbon black composition in an oven at 120 ℃ for 3h before use; the carbon black is kept in an oven at 100 ℃ for 2h before use;
2. adding all the solution polymerized styrene-butadiene rubber into an internal mixer for plasticating for 0.4min, wherein the rotating speed of the internal mixer is 90rpm, and the initial plasticating temperature is 75 ℃;
3. adding the 5/8 white carbon black composition obtained in the step 1 and all softeners into an internal mixer to be mixed for 2min, wherein the weight of the white carbon black composition is 5/8, and the temperature in the internal mixer is controlled not to exceed 140 ℃; then adding the rest white carbon black composition into an internal mixer, and controlling the temperature in the internal mixer within the range of not more than 140 ℃ for mixing for 2 min; unloading the rubber material, and rolling and cutting the rubber material into pieces on a double-roller open mill to obtain a second rubber compound;
4. adding the second rubber compound into an internal mixer and mixing for 2min at the temperature of the internal mixer not more than 140 ℃ under the conditions that the rotating speed of the internal mixer is 90rpm and the initial internal mixing temperature is 75 ℃;
5. adding carbon black, an anti-aging agent and zinc oxide into an internal mixer for mixing, keeping the internal mixing temperature for 5min when reaching 160 ℃, and then unloading the rubber material;
6. passing the rubber material on an open mill with the roller spacing of 5mm and the roller temperature of 50 ℃ for three times; standing for 4 hours by using a mixing adhesive;
7. adjusting the rotation speed of an internal mixer to 60rpm, controlling the temperature to 40 ℃, adding the mixed rubber obtained in the step 6 into the internal mixer, mixing for 30s, adding a vulcanizing agent and a vulcanization accelerator, mixing the rubber, and unloading the rubber when the temperature of the rubber reaches 110 ℃ and is kept at the temperature for 4 min;
8. passing the mixed rubber obtained in the step 7 on an open mill with the roller spacing of 0.5mm and the roller temperature of 50 ℃ for one time, adjusting the roller spacing to 3mm, and passing twice; standing the mixed rubber for 24 hours;
9. vulcanizing the rubber material obtained in the step 8, wherein the vulcanization temperature is 170 ℃, the pressure is 12MPa, and the vulcanization time is determined according to the positive vulcanization time t measured by a rotor-free vulcanizing instrumentc90The determination was 30 min.
As a result, a vulcanized rubber DS3 was obtained.
TABLE 1
Example 1 Example 2 Example 3
SSBR2636 137.5 --- 137.5
SSBR2506 --- 100 ---
TDAE 0 37.5 0
N115 10 --- ---
N234 --- --- 8
N330 --- 15 ---
165GR 60 --- 65
1165MP --- 55 ---
Sulfur 0.5 1.5 2
Accelerator DPG 2 1.5 1.5
Promotion ofAgent TBBS 0 1.5 2.5
ZnO 2 2 3
SA 2 3 4
Si69 4 5 ---
Si75 --- --- 8
Microcrystalline wax 1.5 1 1.5
Antiager RD --- 2 ---
Anti-aging agent MB --- --- 4.5
Anti-aging agent 4010 1.8 --- ---
Test example
The properties of the above vulcanizates S1-S6, DS1-DS3 were tested according to the methods described above, including: mechanical properties, dynamic compression fatigue heating, DIN abrasion and resilience properties, the results are shown in table 2.
TABLE 2
Figure BDA0001138504810000221
As can be seen from Table 2, the vulcanized rubbers obtained by the processes of examples of the present invention are superior to those obtained by the processes of comparative examples in tensile strength, stress at definite elongation, tear strength, heat generation under compression and abrasion resistance, and have excellent overall physical properties. In terms of dynamic mechanical properties, the tan (0 ℃) of the vulcanized rubber obtained by the method of the present invention was higher than that of the vulcanized rubber obtained in the comparative example, and the tan (60 ℃) of the vulcanized rubber obtained by the method of the present invention was lower than that of the vulcanized rubber obtained in the comparative example, that is, the vulcanized rubber obtained by the method of the present invention exhibited good wet skid resistance and low rolling resistance.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (21)

1. A method of preparing a vulcanized rubber, the method comprising:
(1) first mixing a portion of the white carbon black composition and a portion of the host rubber, optionally together with a softening agent, the portion of the white carbon black composition being 2/10 to 9/10 by weight of the total white carbon black composition, the portion of the host rubber being 1/12 to 1/2 by weight of the total host rubber; and then carrying out second mixing on the first mixed rubber obtained after the first mixing and the rest of the white carbon black composition to obtain a second mixed rubber, wherein the white carbon black composition is obtained by premixing white carbon black, a coupling agent and at least part of an activating agent, and the conditions of the first mixing and the second mixing are the same or different and respectively and independently comprise: the temperature is 70-150 deg.C, and the time is 1-8 min; the premixing condition of the white carbon black, the coupling agent and at least part of the activating agent comprises the following steps: the temperature is 5-100 deg.C, and the time is 5-10 min;
(2) and performing third mixing on the rest part of the main rubber and the second mixed rubber to obtain a third mixed rubber, wherein the conditions of the third mixing comprise: the temperature is 70-150 deg.C, and the time is 1-8 min;
(3) performing fourth mixing on the third mixed rubber, carbon black and an anti-aging agent, and optionally a softening agent and/or the rest of an activating agent to obtain a fourth mixed rubber; then, carrying out fifth mixing on the fourth mixed rubber, a vulcanizing agent and a vulcanization accelerator to obtain fifth mixed rubber; the fourth mixing conditions include: the temperature is 150 ℃ and 170 ℃, and the time is 4-10 min; the fifth mixing conditions include: the temperature is 40-110 deg.C, and the time is 1-7 min;
(4) vulcanizing the fifth rubber compound,
the main rubber is styrene butadiene rubber;
relative to 100 parts by weight of the main rubber, the white carbon black is 55-65 parts by weight, the carbon black is 5-15 parts by weight, the softener is 0-25 parts by weight, the coupling agent is 4-8 parts by weight, the anti-aging agent is 3-11 parts by weight, the vulcanizing agent is 0.5-2 parts by weight, the vulcanization accelerator is 2-5 parts by weight, and the activator is 4-8 parts by weight.
2. The method of claim 1, wherein the portion of the white carbon composition is 1/2 to 3/4 by weight of the total white carbon composition.
3. The method of claim 1 wherein the portion of body rubber is 1/4 to 1/3 of the total body rubber weight.
4. The method according to any one of claims 1-3, wherein in step (4), the vulcanization conditions include: the temperature is 150 ℃ and 170 ℃, the pressure is 10-15MPa, and the time is 10-50 min.
5. The method according to any one of claims 1-3, wherein the method further comprises: in the step (1) and the step (2), before the main rubber is used, the main rubber is plasticated at an initial temperature of 75-85 ℃ for 0.4-0.6 min.
6. The method of claim 1, wherein the styrene-butadiene rubber is solution-polymerized styrene-butadiene rubber and/or emulsion-polymerized styrene-butadiene rubber.
7. The method according to any one of claims 1 to 3, wherein the carbon black has an iodine absorption value of not less than 80g/kg, an average particle diameter of 10 to 40 nm and a specific surface area of 80 to 140m2/g。
8. According to any one of claims 1 to 3The method, wherein the specific surface area of the white carbon black is 100-200m2/g。
9. The method as claimed in claim 8, wherein the silica white has a specific surface area of 115-200m2/g。
10. The method according to any one of claims 1 to 3, wherein the softener is a petroleum-based softener.
11. The method according to any one of claims 1 to 3, wherein the softening agent is an aromatic oil and/or a naphthenic oil.
12. The method of any of claims 1-3, wherein the coupling agent is a silane coupling agent.
13. The method of claim 12, wherein the silane coupling agent is at least one of bis- [ gamma- (triethoxysilyl) propyl ] -tetrasulfide, gamma-aminopropyltriethoxysilane, and bis- [ gamma- (triethoxysilyl) propyl ] -disulfide.
14. The method according to any one of claims 1 to 3, wherein the antioxidant is selected from at least one of microcrystalline wax, an amine antioxidant and a quinoline antioxidant.
15. The process according to any one of claims 1 to 3, wherein the antioxidant is a mixture of microcrystalline wax and at least one substance selected from the group consisting of antioxidant RD, antioxidant MB and antioxidant 4010.
16. The method according to claim 15, wherein the content weight ratio of the microcrystalline wax to at least one substance selected from the group consisting of antioxidant RD, antioxidant MB, and antioxidant 4010 is 1: 1.2-3.
17. A process according to any one of claims 1 to 3, wherein the vulcanising agent is sulphur.
18. The method according to any one of claims 1 to 3, wherein the vulcanization accelerator is at least one of diphenylguanidine, N-tert-butyl-2-benzothiazylsulfenamide, 2' -dibenzothiazyl disulfide, N-tert-butyl-bis (2-benzothiazole) sulfenimide, and N-cyclohexyl-bis (2-mercaptobenzothiazole) sulfenamide.
19. The method of any of claims 1-3, wherein the activator is at least one of zinc oxide, magnesium oxide, and stearic acid.
20. A vulcanized rubber produced by the process of any one of claims 1-19.
21. Use of the vulcanizate of claim 20 in the manufacture of a tire.
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CN110435031B (en) * 2019-07-29 2021-12-17 怡维怡橡胶研究院有限公司 Rubber mixing processing technology for improving hardness, increasing modulus and improving tear resistance
CN112847870B (en) * 2021-01-14 2022-06-28 中策橡胶集团股份有限公司 White carbon black-containing rubber composition and mixing method thereof
CN118222019B (en) * 2024-03-11 2025-08-26 怡维怡橡胶研究院有限公司 Zinc-free rubber composition, tread rubber, and preparation method and application thereof

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CN102634077A (en) * 2012-05-02 2012-08-15 三角轮胎股份有限公司 Tire tread rubber composition and preparation method
CN104985710A (en) * 2015-07-01 2015-10-21 特拓(青岛)轮胎技术有限公司 Process for mixing tire tread with high white carbon black content

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CN102634077A (en) * 2012-05-02 2012-08-15 三角轮胎股份有限公司 Tire tread rubber composition and preparation method
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