CN108003408A - One kind vulcanization rubber and its preparation method and application - Google Patents
One kind vulcanization rubber and its preparation method and application Download PDFInfo
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- CN108003408A CN108003408A CN201610934758.1A CN201610934758A CN108003408A CN 108003408 A CN108003408 A CN 108003408A CN 201610934758 A CN201610934758 A CN 201610934758A CN 108003408 A CN108003408 A CN 108003408A
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- Prior art keywords
- rubber
- kneaded
- white carbon
- vulcanization
- temperature
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 228
- 239000005060 rubber Substances 0.000 title claims abstract description 228
- 238000004073 vulcanization Methods 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 93
- 150000001875 compounds Chemical class 0.000 claims abstract description 93
- 238000000034 method Methods 0.000 claims abstract description 76
- 239000000203 mixture Substances 0.000 claims abstract description 71
- 238000002156 mixing Methods 0.000 claims abstract description 65
- 239000006229 carbon black Substances 0.000 claims abstract description 37
- 239000004902 Softening Agent Substances 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 27
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 25
- 239000012190 activator Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims description 41
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical group C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 35
- 239000003292 glue Substances 0.000 claims description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- 239000007822 coupling agent Substances 0.000 claims description 13
- 235000021355 Stearic acid Nutrition 0.000 claims description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 11
- 239000008117 stearic acid Substances 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 10
- 239000004200 microcrystalline wax Substances 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 7
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 claims description 7
- 230000003712 anti-aging effect Effects 0.000 claims description 7
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical group C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 5
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims 2
- 150000003851 azoles Chemical class 0.000 claims 1
- 229930192474 thiophene Natural products 0.000 claims 1
- 238000010057 rubber processing Methods 0.000 abstract description 2
- 238000004513 sizing Methods 0.000 description 32
- 239000003921 oil Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 241000894007 species Species 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 2
- 229920006978 SSBR Polymers 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 210000000481 breast Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004154 testing of material Methods 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 sulphonyl Amine Chemical class 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
Landscapes
- 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 present invention relates to rubber processing application field, discloses a kind of vulcanization rubber and its preparation method and application, this method includes：(1) by a part of white carbon composition and a part of main rubber or and the first mixing of softening agent progress；Then the first rubber compound obtained after first is kneaded carries out second with remaining white carbon composition and is kneaded, and obtains the second rubber compound；(2) remaining main rubber and second rubber compound are carried out the 3rd to be kneaded, obtains the 3rd rubber compound；(3) by the 3rd rubber compound and carbon black and antioxidant or and carry out the 4th with softening agent and/or remainder activator and be kneaded, obtain the 4th rubber compound；Then the 4th rubber compound and vulcanizing agent and vulcanization accelerator are carried out the 5th to be kneaded, obtains the 5th rubber compound；(4) the 5th rubber compound is vulcanized.The present invention can obtain it is a kind of there is excellent mechanical property, low-heat-generation, low-rolling-resistance, the vulcanization rubber of good wet-sliding resistant performance and excellent wear-resisting property.
Description
Technical field
The present invention relates to rubber processing application field, and in particular, to it is a kind of prepare vulcanization rubber method and by this
Application of the vulcanization rubber, foregoing vulcanization rubber that method is prepared in tire is prepared.
Background technology
With world energy sources crisis and the aggravation of environmental pollution, various countries are to energy saving and environmentally friendly increasingly pay attention to.In order to reduce
The consumption of fuel oil and the discharge of greenhouse gases, auto industry also develop towards energy saving and environmentally friendly direction.
2009, European Union promulgated two new legislations for being related to tire, it is desirable to farthest improves tire safety, subtracts
Few oil consumption, reduce noise.This performance to tire proposes the requirement of higher, it is desirable to which tire is ensureing high distance travelled (tyre surface
It is wear-resisting) on the premise of road pavement grasp property it is good, the wet-sliding resistant performance especially on rainy day wet-skid road surface and ice and snow road
It is good.And high-performance tire then requires low-rolling-resistance, good wet-sliding resistant performance and excellent wear-resisting property.
At the end of the 20th century, Michelin proposes the concept of " green tire ", refers to being matched somebody with somebody with white carbon alternative tires tread rubber
Carbon black in side declines tire drag, oil consumption is reduced, and reaches motor vehicle emission reduction and energy-saving and emission-reduction as reinforcing agent
Purpose.
《Rubber industry》(2012,2:84-90) comparative study is mended respectively using the carbon black and white carbon of same volume fraction
The performance of strong solution polymerized butadiene styrene rubber and emulsion polymerized styrene butadiene rubber tread rubber.The result shows that：Compared with carbon black filled butadiene-styrene rubber sizing material,
The dispersiveness of white carbon filler gum through coupling agent Si69 heat treatments improves, and vulcanizes the 300% stress at definite elongation increase of rubber, draws
Disconnected elongation reduces, and wet-sliding resistant performance improves, and rolling resistance and dynamic heat build up reduce, wear-resisting property and anti-cut poor-performing.
《Tire industry》(2007,1:25-30) inquired into silica/carbon black and with comparing emulsion polymerized styrene butadiene rubber
The influence of ESBR1721 and solution polymerized butadiene styrene rubber SSBR Y837V2 passenger car tire treads colloidality energy.The result shows that with hard charcoal
Black/carbon black and with than increase, the tan δ values and rolling loss during ESBR1721 and SSBR Y837V2 60 DEG C of rubber of vulcanization be linear
Decline, the tan δ values and lateral factor linear increment, wear-resisting property at 0 DEG C are declined slightly.
White carbon of the green tire production because largely using high structure in formula, white carbon are not easy to disperse when being kneaded, and
Volume can improve the hardness of sizing material when coordinating, heat is larger during mixing, so process implementing and difficult processing in tire production process
Degree is very big.
Therefore, it is necessary to develop a kind of new processing technology that there is excellent mechanical property, low life to obtain one kind in practice
Heat, low-rolling-resistance, the vulcanization rubber of good wet-sliding resistant performance and excellent wear-resisting property.
The content of the invention
The object of the present invention is to provide a kind of method of new preparation vulcanization rubber, there is excellent mechanical property to obtain one kind
Can, low-heat-generation, low-rolling-resistance, the vulcanization rubber of good wet-sliding resistant performance and excellent wear-resisting property.
To achieve these goals, in a first aspect, the present invention provides a kind of method for preparing vulcanization rubber, this method bag
Include：
(1) by a part of white carbon composition and a part of main rubber optionally and softening agent carry out first be kneaded；
Then the first rubber compound obtained after first is kneaded carries out second with remainder white carbon composition and is kneaded, and it is mixed to obtain second
Refining glue, the white carbon composition are pre-mixed by white carbon, coupling agent and at least part activator and are obtained；
(2) remainder main rubber and second rubber compound are carried out the 3rd to be kneaded, obtains the 3rd rubber compound；
(3) the 3rd rubber compound and carbon black and antioxidant optionally and with softening agent and/or remainder are activated
Agent carries out the 4th and is kneaded, and obtains the 4th rubber compound；Then the 4th rubber compound and vulcanizing agent and vulcanization accelerator are carried out the
Five are kneaded, and obtain the 5th rubber compound；
(4) the 5th rubber compound is vulcanized.
Second aspect, the present invention provide a kind of vulcanization rubber being prepared by preceding method.
The third aspect, the present invention provide the vulcanization rubber described in a kind of first aspect.
Fourth aspect, the present invention provide application of the foregoing vulcanization rubber in tire is prepared.
The technique of the invention for vulcanizing rubber by providing a kind of new preparation, which can obtain one kind, has excellent mechanical property,
Low-heat-generation, low-rolling-resistance, the vulcanization rubber of good wet-sliding resistant performance and excellent wear-resisting property.
Also, the vulcanization rubber phase that the method provided by the present invention for preparing vulcanization rubber obtains for making in the prior art
The vulcanization rubber that the method for standby vulcanization rubber obtains has more preferable comprehensive physical mechanical performance and dynamic mechanical.
Further, the method provided by the invention for preparing vulcanization rubber also has the advantages that simple process and low cost is honest and clean.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
First aspect, the present invention provides a kind of method for preparing vulcanization rubber, this method includes：
(1) by a part of white carbon composition and a part of main rubber optionally and softening agent carry out first be kneaded；
Then the first rubber compound obtained after first is kneaded carries out second with remainder white carbon composition and is kneaded, and it is mixed to obtain second
Refining glue, the white carbon composition are pre-mixed by white carbon, coupling agent and at least part activator and are obtained；
(2) remainder main rubber and second rubber compound are carried out the 3rd to be kneaded, obtains the 3rd rubber compound；
(3) the 3rd rubber compound and carbon black and antioxidant optionally and with softening agent and/or remainder are activated
Agent carries out the 4th and is kneaded, and obtains the 4th rubber compound；Then the 4th rubber compound and vulcanizing agent and vulcanization accelerator are carried out the
Five are kneaded, and obtain the 5th rubber compound；
(4) the 5th rubber compound is vulcanized.
" a part of white carbon composition " and " remainder white carbon composition " form whole hard charcoals of the present invention
Black composition.
" a part of main rubber " and " remainder main rubber " form whole main rubbers of the present invention.
In the step (1), " optionally and softening agent " refers to that in step (1) softening agent can be added, can also
It is added without softening agent.Whether those skilled in the art can be according to oil-filled in main rubber, and determine whether should for oil-filled number
The addition softening agent.
In step (3), " by the 3rd rubber compound and carbon black and antioxidant optionally and with softening agent and/or surplus
Remaining partial activation agents progress the 4th is kneaded " refer to, participating in the 4th material being kneaded can be the 3rd rubber compound, carbon black and prevent old
Agent；Or it can be the 3rd rubber compound, carbon black, antioxidant and softening agent to participate in the 4th material being kneaded；Or participate in the 4th and mix
The material of refining can be the 3rd rubber compound, carbon black, antioxidant and remainder activator；Or the material that participation the 4th is kneaded can
Think the 3rd rubber compound, carbon black, antioxidant, softening agent and remainder activator.Softening in the step of before step (3)
When the dosage of agent is inadequate, proper amount of softening agent can be added in step (3), alternatively, involved in the method for the present invention
Softening agent can be added without, once be added in step (1), once be added in step (3), or in step (1) and step
(3) it is added portionwise in.And the remainder activator optionally contained represents, the activation in the white carbon composition of step (1)
When agent is only the part in whole activators, the activator of remainder is added in the step (3).
The vulcanization rubber that method provided by the present invention is prepared has excellent wet-sliding resistant performance, while has rolling
Excellent properties and the good comprehensive physical mechanical performances such as resistance is low, compression temperature rise is low, abrasion are small.
Preferably, a part of white carbon composition accounts for 2/10 to the 9/10 of whole white carbon composition weights；It is more excellent
Selection of land, a part of white carbon composition account for 1/2 to the 3/4 of whole white carbon composition weights；The present inventor sends out
Existing, the weight for controlling the white carbon composition added for the first time is 2/10 to the 9/10 of whole white carbon composition weights, preferably
When accounting for 1/2 to 3/4, the vulcanization rubber obtained by the method for the present invention has more preferable dynamic mechanical.
Preferably, a part of main rubber accounts for 1/12 to the 1/2 of whole main rubber weight；It is it is highly preferred that described
A part of main rubber accounts for 1/4 to the 1/3 of whole main rubber weight；It was found by the inventors of the present invention that control adds for the first time
The weight of main rubber be 1/12 to the 1/2 of whole main rubber weight, when being preferably 1/4 to 1/3, by the method for the present invention
The vulcanization rubber of acquisition has more preferable dynamic mechanical.
Preferably, in step (1), first mixing and the described second condition being kneaded are identical or different, each solely
On the spot include：Temperature is 70-150 DEG C, time 1-8min.It is highly preferred that the described first temperature being kneaded is 70-150 DEG C, when
Between be 2-4min；Described second temperature being kneaded is 70-150 DEG C, time 2-4min.
Preferably, in step (2), the described 3rd condition being kneaded includes：Temperature is 70-150 DEG C, time 1-
8min.It is highly preferred that the described 3rd condition being kneaded includes：Temperature is 70-150 DEG C, time 2-4min.
In the present invention, when the temperature in first mixing, the second mixing and the 3rd mixing process can be with being kneaded
Between change and change, as long as can control it is described first be kneaded, second be kneaded and the 3rd be kneaded in temperature before this invention
State in the range of defining.
Preferably, in step (3), the described 4th condition being kneaded includes：Temperature is 150-170 DEG C, time 4-
10min；It is highly preferred that the described 4th condition being kneaded includes：Temperature is 150-170 DEG C, time 5-7min.
Preferably, in step (3), the described 5th condition being kneaded includes：Temperature is 40-110 DEG C, time 1-
7min；It is highly preferred that the described 5th condition being kneaded includes：Temperature is 40-110 DEG C, time 3-5min.
According to the present invention, usually, the method and condition the 5th rubber compound vulcanized is those skilled in the art
It is known.For example, the vulcanization can carry out in vulcanization bed or vulcanizing press；The conditions of vulcanization generally includes vulcanization temperature
Degree, sulfide stress and vulcanization time, wherein, as long as the curing temperature, sulfide stress and vulcanization time can ensure the master
Body rubber and vulcanizing agent crosslink reaction, for example, the condition of the vulcanization reaction can be including curing temperature
150-170 DEG C, sulfide stress can be 10-15MPa, and vulcanization time can be 10-50 minutes.
Preferably, in step (1), condition bag that white carbon, coupling agent and at least part activator are pre-mixed
Include：Temperature is 5-100 DEG C, time 5-10min.
Further, method of the invention can also include, first will premixing before using the white carbon composition
The white carbon composition obtained afterwards heats 0.5-5h under conditions of 80-150 DEG C.
And method of the invention can also include, before using the carbon black, first by bar of the carbon black at 80-150 DEG C
0.5-5h is heated under part.
Preferably, method of the invention further comprises：In step (1) and step (3), the main rubber is being used
Before, first by the main rubber be 75-85 DEG C in initial temperature at plasticate 0.4-0.6min.
Preferably, relative to the main rubber of 100 parts by weight, the dosage of the white carbon is 55-65 parts by weight, institute
The dosage for stating carbon black is 5-15 parts by weight, and the dosage of the softening agent is 0-25 parts by weight, and the dosage of the coupling agent is 4-8 weights
Part is measured, the dosage of the antioxidant is 3-11 parts by weight, and the dosage of the vulcanizing agent is 0.5-2 parts by weight, and the vulcanization promotes
The dosage of agent is 2-5 parts by weight, and the dosage of the activator is 4-8 parts by weight.When the main rubber is oil-extended rubber, and fill
When filling oil content in oily rubber is enough, the dosage of the softening agent can be 0.In the present invention, softening agent is optional
Species is identical with the optional species of filling oil.
In the present invention, unless stated otherwise, otherwise " relative to the main rubber of 100 parts by weight " in 100 weights
The main rubber of amount part is the parts by weight for filling oil for not including wherein containing.That is, work as the main body rubber
It is the content for not including filling oil when the main rubber oil-filled using this is as benchmark when in glue containing filling oil.This area skill
Art personnel should not be construed as limiting the invention.
Preferably, the main rubber is butadiene-styrene rubber.More preferably described butadiene-styrene rubber is solution polymerized butadiene styrene rubber and/or breast
Poly- butadiene-styrene rubber.
It is particularly preferred that the butadiene-styrene rubber gathers selected from oil-filled solution polymerized butadiene styrene rubber, non-oil-filled solution polymerized butadiene styrene rubber and breast
At least one of butadiene-styrene rubber.
, can in step of the invention (1) and/or step (3) when the butadiene-styrene rubber is non-oil-filled solution polymerized butadiene styrene rubber
To use softening agent.
Preferably, the oil-filled solution polymerized butadiene styrene rubber combinated styrene content content is 23-28 weight %；Contents of ethylene is
55-66 weight %；Mooney viscosity is 55-67；Oil-filled number is 15-37.5phr.
Preferably, the non-oil-filled solution polymerized butadiene styrene rubber combinated styrene content content is 20-30 weight %；Contents of ethylene is
50-60 weight %；Mooney viscosity is 60-68.
Preferably, the emulsion polymerized styrene butadiene rubber combinated styrene content content is 22-25 weight %；Mooney viscosity is 45-60；Fill
Oil content number is 0-50phr.
Preferably, the iodine absorption value of the carbon black is not less than 80g/kg, and average particulate diameter is 10-40 nanometers, specific surface area
For 80-140m2/g。
Preferably, the specific surface area of the white carbon is 100-200m2/ g, more preferably 115-200m2/g。
Preferably, the softening agent is petroleum line softener, more preferably aromatic naphtha and/or naphthenic oil.It is such as described soft
Agent can be that TDAE (processed aromatic naphtha (Treated Distillate Aromatic Extract)), RAE are (remaining
At least one of Aromatic raffinate (Residual Aromatic Extract)) and NAP (naphthenic oil (Napthtenics)).
There is no particular limitation for property of the present invention to the aromatic naphtha and the naphthenic oil, can be each of ordinary meaning in the art
The kind aromatic naphtha and the naphthenic oil.
Preferably, the coupling agent is silane coupling agent, it is highly preferred that the coupling agent is Si69 (double-[γ-(three second
Epoxide silicon) propyl group]-tetrasulfide), KH550 (gamma-aminopropyl-triethoxy-silane) and Si75 (double-[γ-(triethoxysilicanes)
At least one of propyl group]-disulphide).
Preferably, the antioxidant is selected from least one of microwax, amines antioxidants and quinoline type antioxidant.It is more excellent
Selection of land, the antioxidant is for microwax and selected from 2,2,4- trimethyl -1,2- dihyaroquinoline condensates (anti-aging agent RD), 2- mercaptos
At least one of base benzimidazole (antioxidant MB) and N- cyclohexyl-N '-diphenyl-para-phenylene diamine (antioxidant 4010) material
Mixture.
When the antioxidant is for microwax and selected from least one of anti-aging agent RD, antioxidant MB and antioxidant 4010 thing
During the mixture of matter, preferably described microwax is with being selected from least one of anti-aging agent RD, antioxidant MB and antioxidant 4010 thing
The content weight ratio of matter is 1：1.2-3.
Preferably, the vulcanizing agent is sulphur.
Preferably, the vulcanization accelerator is diphenylguanidine (diphenylguanidine PG), the N- tert-butyl groups -2-[4-morpholinodithio base time sulphonyl
Amine (accelerator TBBS), 2,2'- dibenzothiazyl disulfides, the N- tert-butyl groups-bis- (2-[4-morpholinodithio) sulfenamide and N- rings
At least one of hexyl-bis- (2-mercaptobenzothiazole) sulfenamide.
Preferably, the activator is at least one of zinc oxide, magnesia and stearic acid.
According to a kind of preferred embodiment, the method for the preparation of the invention vulcanization rubber includes：
1st, white carbon, coupling agent and at least part activator are pre-mixed 5-10min at 5-100 DEG C, obtain white carbon
Composition, and before use, the white carbon composition is heated into 0.5-5h under conditions of 80-150 DEG C；And using
It is preceding that carbon black is heated into 0.5-5h under conditions of 80-150 DEG C；
2nd, by a part of white carbon composition and a part of main rubber optionally and softening agent carry out first be kneaded；So
The first rubber compound obtained after first is kneaded afterwards carries out second with remainder white carbon composition and is kneaded, and obtains the second mixing
Glue；Wherein, a part of white carbon composition accounts for 1/2 to the 3/4 of whole white carbon composition weights, and a part of main rubber accounts for entirely
1/4 to the 1/3 of portion's main rubber weight；First mixing and the described second condition being kneaded are identical or different, each independent
Ground includes：Temperature is 70-150 DEG C, time 1-8min；
3rd, remainder main rubber and second rubber compound are carried out the 3rd to be kneaded, obtains the 3rd rubber compound；It is described
3rd condition being kneaded includes：Temperature is 70-150 DEG C, time 1-8min；
4th, by the 3rd rubber compound and carbon black and antioxidant optionally and softening agent and remainder activator carry out
4th is kneaded, and obtains the 4th rubber compound；Then the 4th rubber compound and vulcanizing agent and vulcanization accelerator are carried out the 5th to be kneaded,
Obtain the 5th rubber compound；Wherein, the described 4th condition being kneaded includes：Temperature is 150-170 DEG C, time 4-10min；It is described
5th condition being kneaded includes：Temperature is 40-110 DEG C, time 1-7min；
5th, the 5th rubber compound is vulcanized；It is 150-170 DEG C that the condition of the vulcanization reaction, which includes curing temperature,
Sulfide stress is 10-15MPa, and vulcanization time is 10-50 minutes；And
In step (1) and step (3), before using the main rubber, first by the main rubber at 75-85 DEG C
Under plasticate 0.4-0.6min.
A kind of preferred embodiment according to the present invention, the preparation of the invention vulcanize the method bag of rubber
Include：
1st, white carbon, coupling agent and at least part activator are pre-mixed 5-10min at 5-100 DEG C, obtain white carbon
Composition, and before use, the white carbon composition is heated into 0.5-5h under conditions of 80-150 DEG C；And using
It is preceding that carbon black is heated into 0.5-5h under conditions of 80-150 DEG C；
2nd, a part of main rubber is added into mixer the 0.4-0.6min that plasticates, wherein, banbury rotating speed 85-
95rpm, mixing initial temperature are 75-85 DEG C；
3rd, a part of white carbon composition and whole softening agents are added in mixer, and first is carried out at 70-150 DEG C
2-4min is kneaded, obtains the first rubber compound；Then remainder white carbon composition is added in mixer, and at 70-150 DEG C
It is lower to carry out the second mixing 2-4min；Sizing material is unloaded, roller is crossed in two-roll mill and cuts out block, obtains the second rubber compound；
4th, remainder main rubber is added in mixer and plasticated 0.4-0.6min, banbury rotating speed 85-95rpm is close
It is 75-85 DEG C to refine initial temperature；Then second rubber compound is added and carries out the 3rd mixing in mixer at 70-150 DEG C,
Mixing time is 1-8min, obtains the 3rd rubber compound；
5th, carbon black and antioxidant optionally and in remaining activator addition mixer are subjected to the 4th mixing, treat mixing
Temperature reaches to be kept unloading the 4th rubber compound of gained during 4-10min at 150-170 DEG C；
6th, it is 4-6mm in roll spacing by the 4th rubber compound, by three times on the open mill that roller temperature is 50 ± 5 DEG C；Batch mixing
Glue parks 3.5-4.5h；
7th, banbury rotating speed is adjusted to 55-65rpm, temperature is adjusted to 40 ± 5 DEG C, and the batch mixing glue that step 6 obtains is added
Enter to be kneaded 20-60s in mixer and add the 5th mixing of vulcanizing agent and vulcanization accelerator progress afterwards, when sizing material temperature reaches 110-
120 DEG C and at such a temperature keep 1-7min when unload gained the 5th rubber compound；
8th, it is 0.4-0.6mm in roll spacing by the 5th rubber compound, by once on the open mill that roller temperature is 50 ± 5 DEG C,
Then roll spacing is adjusted to 2-4mm, then by twice；Rubber compound parks 20-28h；
9th, the sizing material obtained after step 8 is vulcanized, conditions of vulcanization includes：Curing temperature is 150-170 DEG C, pressure
10-15MPa, the sulfurizing time t that vulcanization time is measured according to no rotor vulcameterc90Determine.
Second aspect, a kind of vulcanization rubber being prepared by preceding method of present invention offer.
The third aspect, the vulcanization rubber described in a kind of first aspect of present invention offer.
In the third aspect of the present invention, the vulcanization rubber refers to the method preparation by the first aspect of the present invention
The vulcanization rubber of the property of obtained vulcanization rubber, and and must be by this not as defined in the second aspect of the present invention
The method of the first aspect of invention is prepared.That is, to the preparation method for vulcanizing rubber in the third aspect of the present invention simultaneously
Do not limit, as long as it is the 3rd of the present invention that can obtain the product identical with the vulcanization rubber properties described in first aspect
Vulcanization rubber described in aspect.
Fourth aspect, application of the foregoing vulcanization rubber of present invention offer in tire is prepared.
The present invention will be described in detail by way of examples below.
The performance of the vulcanization rubber of the present invention is tested as follows：
Mechanical property：Mechanical property is carried out to material prepared using Material Testing Machine (SHIMADZU, AG-20KNG)
Test characterization.Force snesor selected by Material Testing Machine is 1KN.According to national standard GB/T 528-2009, rate of extension is
500mm/min, test temperature are 23 ± 2 DEG C.The live part length of sample is 25mm, width 6mm.For every group of sample,
5 parallel laboratory tests are carried out, results are averaged.
Dynamic mechanical：Temperature scanning is enterprising in German GABO companies EPLEXOR 500N dynamic thermomechanical analysis apparatus
OK, using stretching clamp, test frequency 11Hz, temperature range：Subzero 80 DEG C to 80 DEG C above freezing, heating rate is 3 DEG C/min,
Static strain is 1%, dynamic strain 0.25%.
Dynamic compression heat build-up：By GB/T 1687-1993, using the production of Beijing You Shen Electron equipment Co., Ltd
The dynamic compression heat build-up of RH-2000 type rubber compression heat generation testing machine test samples.Test condition：Stroke is 4.45mm,
Load is 1MPa, and temperature is 55 DEG C, time 25min.
DIN is worn away：According to national standard《(rotating roller cartridge type is worn away the measure of GB/T 9867-2008 vulcanization rubber wear-resisting performances
Machine method)》Regulation, using the test of DIN abrasion instruments (GT-7012-D, TaiWan, China high ferro instrument detection Co., Ltd) vulcanization rubber
Relative volume abrasion loss.
Resilience performance：Using the high Inland Steel GT-7042-RE types caoutchouc elasticity testing machine of TaiWan, China, according to national standard《GB/T
1681-2009 vulcanization resilience of vulcanizate measure》Measure resilience performance.
The vulcanization characteristics of rubber compound：Measured by GB/T 16584-1996 standards using no rotor vulcameter, test temperature is
160℃。
In the present invention, the specific surface area measures to obtain using BET specific surface area method.
Material source used below is：
It purchased from the trade mark of Yanshan Mountain branch company of Sinopec Group is SSBR2636 that butadiene-styrene rubber (SBR), which is,
With the commodity of SSBR2506, wherein, SSBR2636 (oil-filled solution polymerized butadiene styrene rubber) combinated styrene content content is 25 weight %, ethene
Base content is 63 weight %, and Mooney viscosity 62, oil-filled number is 37.5phr；SSBR2506 (non-oil-filled solution polymerized butadiene styrene rubber)
Combinated styrene content is 26 weight %, and contents of ethylene is that 56 weight % Mooney viscosities are 65, and oil-filled number is 0phr.
It purchased from the hundred million Bo Rui Chemical Co., Ltd.s trade mark of Tianjin is that (iodine absorption value 160g/kg, specific surface area are N115 that carbon black, which is,
137m2/ g), N234 (iodine absorption value 120g/kg, specific surface area 119m2/ g), N330 (iodine absorption value 82g/kg, specific surface area
For 78m2/ g) commodity.
White carbon is to tie up the polymolecularity that fine chemistry industry additive (Qingdao) Co., Ltd trade mark is 165GR purchased from Sol
Grain white carbon and the trade mark are the commodity of the high-ratio surface microballon white carbon of 1165MP, and specific surface area is 165m2/g。
Sulphur (vulcanizing agent) is the commodity purchased from Sinopharm Chemical Reagent Co., Ltd..
Diphenylguanidine (vulcanization accelerator) is the commodity purchased from Shijiazhuang City first rays of the morning sun Chemical Co., Ltd..
Accelerator TBBS (vulcanization accelerator) is the commodity purchased from Guangdong Du Ba new materials Science and Technology Ltd..
ZnO (activator) is the commodity purchased from Sinopharm Chemical Reagent Co., Ltd..
SA (stearic acid) (activator) is the commodity purchased from Sinopharm Chemical Reagent Co., Ltd..
The commodity that it is W-445 purchased from the Tianjin Heng Shengxin sources International Trading Company Ltd trade mark that microwax, which is, carbon atom number
For 20-50.
Si69 and Si75 (silane coupling agent) is the commodity purchased from Shanghai Rui Shi Chemical Industry Science Co., Ltd.
2,2,4- trimethyl -1,2- dihyaroquinolines condensates (anti-aging agent RD) and 2-mercaptobenzimidazole (antioxidant MB)
For purchased from the commodity of upper marine origin brocade Chemical Co., Ltd..
N- cyclohexyl-N '-diphenyl-para-phenylene diamine (antioxidant 4010) is the business purchased from Gaoyi County profit and Chemical Co., Ltd.
Product.
Softening agent is environment-friendly aromatic oil TDAE purchased from Zibo thousand along plastic cement Co., Ltd, arene content >=85%.
The total amount for the rubber composition that each component of preparation vulcanization rubber involved in following embodiment is formed is identical,
For 1200g.
Embodiment 1：The method for preparing vulcanization rubber S1
(numerical value therein is relative to 100 weights to the formula of each component involved in the method for the present embodiment as shown in table 1
The parts by weight that the main rubber of amount part obtains).The preparation method of the vulcanization rubber S1 of the present embodiment is specific as follows：
1st, at 40 DEG C, white carbon, silane coupling agent and stearic acid are mixed into 10min, Ran Hou in high-speed mixer
3 each 10s are ground in high-speed grinder, obtain white carbon composition, white carbon composition is protected using preceding in 140 DEG C of baking ovens
Warm 2h；Carbon black keeps the temperature 2h in 110 DEG C of baking ovens before use；
2nd, 1/3 solution polymerized butadiene styrene rubber for accounting for whole solution polymerized butadiene styrene rubber weight is added into mixer the 0.5min that plasticates,
Wherein, banbury rotating speed 90rpm, initial temperature of plasticating are 80 DEG C；
3rd, the white carbon composition and whole softening agents obtained 3/4 step 1 for accounting for whole white carbon composition weights
Add in mixer and carry out the first mixing 2min, control the temperature in mixer to be no more than 140 DEG C；Then by the white of remainder
Carbon composition is added in mixer, and controls the second mixing 2min in the range of no more than 140 DEG C of the temperature in mixer；Unload
Lower sizing material, roller sanction block is crossed in two-roll mill, obtains the second rubber compound；
4th, remainder solution polymerized butadiene styrene rubber is added into mixer the 0.5min that plasticates, banbury rotating speed 90rpm, mixing
Initial temperature is 80 DEG C；By second rubber compound add in mixer and control in mixer temperature be no more than at 140 DEG C into
Row the 3rd is kneaded 2min, obtains the 3rd rubber compound；
5th, carbon black, antioxidant and zinc oxide are added in mixer and carries out the 4th mixing, when mixing temperature reaches 150 DEG C
5min is kept, then unloads the 4th rubber compound of gained；
6th, it is 5mm in roll spacing by the 4th rubber compound, by three times on the open mill that roller temperature is 50 DEG C；Batch mixing glue is parked
4h；
7th, banbury rotating speed is adjusted to 60rpm, temperature is 40 DEG C, and the batch mixing glue that step 6 is obtained adds mixer mixing
Vulcanizing agent is added after 30s and vulcanization accelerator carries out the 5th and is kneaded, when sizing material temperature reaches 110 DEG C and keeps at such a temperature
During 4min, the 5th rubber compound of gained is unloaded；
8th, it is 0.5mm in roll spacing by the 5th rubber compound that step 7 obtains, by once on the open mill that roller temperature is 50 DEG C,
Then roll spacing is adjusted to 3mm, then by twice；Rubber compound parks 24h；
9th, the sizing material for obtaining step 8 is vulcanized, wherein, curing temperature is 160 DEG C, pressure 15MPa, vulcanization time
The sulfurizing time t measured according to no rotor vulcameterc90It is determined as 30min.
As a result vulcanization rubber S1 is obtained.
Embodiment 2：The method for preparing vulcanization rubber S2
(numerical value therein is relative to 100 weights to the formula of each component involved in the method for the present embodiment as shown in table 1
The parts by weight that the main rubber of amount part obtains).The preparation method of the vulcanization rubber S2 of the present embodiment is specific as follows：
1st, at 70 DEG C, white carbon, silane coupling agent and stearic acid are mixed into 5min in high-speed mixer, then in height
5 each 8s are ground in fast grinder, obtain white carbon composition, white carbon composition is kept the temperature using preceding in 120 DEG C of baking ovens
3h；Carbon black keeps the temperature 2h in 110 DEG C of baking ovens before use；
2nd, 1/4 solution polymerized butadiene styrene rubber for accounting for whole solution polymerized butadiene styrene rubber weight is added into mixer the 0.4min that plasticates,
Wherein, banbury rotating speed 90rpm, initial temperature of plasticating are 85 DEG C；
3rd, the white carbon composition and whole softening agents obtained 1/2 step 1 for accounting for whole white carbon composition weights
Add in mixer and carry out the first mixing 2min, control the temperature in mixer to be no more than 140 DEG C, obtain the first rubber compound；So
The white carbon composition of remainder is added in mixer afterwards, and controls the temperature in mixer in no more than 140 DEG C scopes
It is interior to carry out the second mixing 2min；Sizing material is unloaded, roller is crossed in two-roll mill and cuts out block, obtains the second rubber compound；
4th, remainder solution polymerized butadiene styrene rubber is added into mixer the 0.4min that plasticates, banbury rotating speed 90rpm, mixing
Initial temperature is 85 DEG C；By second rubber compound add in mixer and control in mixer temperature be no more than at 140 DEG C into
Row the 3rd is kneaded 2min, obtains the 3rd rubber compound；
5th, carbon black, antioxidant and zinc oxide are added in mixer and carries out the 4th mixing, when mixing temperature reaches 160 DEG C
5min is kept, then unloads the 4th rubber compound of gained；
6th, it is 5mm in roll spacing by the 4th rubber compound, by three times on the open mill that roller temperature is 50 DEG C；Batch mixing glue is parked
4h；
7th, banbury rotating speed is adjusted to 60rpm, temperature is 40 DEG C, and the batch mixing glue that step 6 is obtained adds mixer mixing
Vulcanizing agent and vulcanization accelerator are added after 30s, the 5th is carried out and is kneaded, when sizing material temperature reaches 110 DEG C and protects at such a temperature
When holding 4min, the 5th rubber compound of gained is unloaded；
8th, it is 0.5mm in roll spacing by the 5th rubber compound that step 7 obtains, by once on the open mill that roller temperature is 50 DEG C,
Then roll spacing is adjusted to 3mm, then by twice；Rubber compound parks 24h；
9th, the sizing material for obtaining step 8 is vulcanized, wherein, curing temperature is 150 DEG C, pressure 14MPa, vulcanization time
The sulfurizing time t measured according to no rotor vulcameterc90It is determined as 30min.
As a result vulcanization rubber S2 is obtained.
Embodiment 3：The method for preparing vulcanization rubber S3
(numerical value therein is relative to 100 weights to the formula of each component involved in the method for the present embodiment as shown in table 1
The parts by weight that the main rubber of amount part obtains).The preparation method of the vulcanization rubber S3 of the present embodiment is specific as follows：
1st, at 60 DEG C, white carbon, silane coupling agent and stearic acid are mixed into 5min in high-speed mixer, then in height
4 each 10s are ground in fast grinder, obtain white carbon composition, white carbon composition is kept the temperature using preceding in 120 DEG C of baking ovens
3h；Carbon black keeps the temperature 2h in 100 DEG C of baking ovens before use；
2nd, 7/24 solution polymerized butadiene styrene rubber for accounting for whole solution polymerized butadiene styrene rubber weight is added into mixer the 0.4min that plasticates,
Wherein, banbury rotating speed 90rpm, initial temperature of plasticating are 75 DEG C；
3rd, the white carbon composition and whole softening agents obtained 5/8 step 1 for accounting for whole white carbon composition weights
Add in mixer and carry out the first mixing 2min, control the temperature in mixer to be no more than 140 DEG C, obtain the first rubber compound；So
The white carbon composition of remainder is added in mixer afterwards, and controls the temperature in mixer in no more than 140 DEG C scopes
It is interior to carry out the second mixing 2min；Sizing material is unloaded, roller is crossed in two-roll mill and cuts out block, obtains the second rubber compound；
4th, remainder solution polymerized butadiene styrene rubber is added into mixer the 0.4min that plasticates, banbury rotating speed 90rpm, mixing
Initial temperature is 75 DEG C；By second rubber compound add in mixer and control in mixer temperature be no more than at 140 DEG C into
Row the 3rd is kneaded 2min, obtains the 3rd rubber compound；
5th, carbon black, antioxidant and zinc oxide are added in mixer and carries out the 4th mixing, when mixing temperature reaches 160 DEG C
5min is kept, then unloads the 4th rubber compound of gained；
6th, it is 5mm in roll spacing by the 4th rubber compound, by three times on the open mill that roller temperature is 50 DEG C；Batch mixing glue is parked
4h；
7th, banbury rotating speed is adjusted to 60rpm, temperature is 40 DEG C, and the batch mixing glue that step 6 is obtained adds mixer mixing
Vulcanizing agent and vulcanization accelerator are added after 30s, the 5th is carried out and is kneaded, when sizing material temperature reaches 110 DEG C and protects at such a temperature
When holding 4min, the 5th rubber compound of gained is unloaded；
8th, it is 0.5mm in roll spacing by the 5th rubber compound that step 7 obtains, by once on the open mill that roller temperature is 50 DEG C,
Then roll spacing is adjusted to 3mm, then by twice；Rubber compound parks 24h；
9th, the sizing material for obtaining step 8 is vulcanized, wherein, curing temperature is 170 DEG C, pressure 12MPa, vulcanization time
The sulfurizing time t measured according to no rotor vulcameterc90It is determined as 30min.
As a result vulcanization rubber S3 is obtained.
Embodiment 4：The method for preparing vulcanization rubber S4
The present embodiment is carried out using method similar to Example 1, except that：
In the present embodiment, a part of main rubber first added accounts for the 1/6 of whole main rubber gross weights, remaining with reality
Apply identical in example 1.
That is, the species and total dosage of each component involved in the method for the present embodiment are in the same manner as in Example 1.
Obtain vulcanization rubber S4.
Embodiment 5：The method for preparing vulcanization rubber S5
The present embodiment is carried out using method similar to Example 2, except that：
In the present embodiment, a part of white carbon composition first added accounts for the 3/10 of whole white carbon composition total weights,
Remaining is in the same manner as in Example 2.
That is, the species and total dosage of each component involved in the method for the present embodiment are in the same manner as in Example 2.
Obtain vulcanization rubber S5.
Embodiment 6：The method for preparing vulcanization rubber S6
The present embodiment is carried out using method similar to Example 4, except that：
In the present embodiment, a part of white carbon composition first added accounts for the 3/10 of whole white carbon composition total weights,
Remaining is in the same manner as in Example 4.
That is, the species and total dosage of each component involved in the method for the present embodiment are in the same manner as in Example 4.
Obtain vulcanization rubber S6.
Comparative example 1：The method for preparing vulcanization rubber DS1
This comparative example is carried out using method similar to Example 1, the difference is that the white carbon combination in this comparative example
Thing and main rubber are a feed postition, specifically：
1st, at 40 DEG C, white carbon, silane coupling agent and stearic acid are mixed into 10min, Ran Hou in high-speed mixer
3 each 10s are ground in high-speed grinder, obtain white carbon composition, white carbon composition is protected using preceding in 140 DEG C of baking ovens
Warm 2h；Carbon black keeps the temperature 2h in 110 DEG C of baking ovens before use；
2nd, whole solution polymerized butadiene styrene rubbers are added into mixer the 0.5min that plasticates, wherein, banbury rotating speed 90rpm, modeling
It is 80 DEG C to refine initial temperature；
3rd, white carbon composition and whole softening agent that step 1 obtains are added in mixer and is kneaded 2min, control mixing
Temperature in machine is no more than 140 DEG C；Sizing material is unloaded, roller is crossed in two-roll mill and cuts out block, obtains the second rubber compound；
4th, it is 90rpm in banbury rotating speed, under the conditions of mixing initial temperature is 80 DEG C, second rubber compound is added close
In mill and temperature in mixer is controlled to be no more than 140 DEG C of mixing 2min；
5th, carbon black, antioxidant and zinc oxide are added in mixer and is kneaded, kept when mixing temperature reaches 150 DEG C
5min, then unloads sizing material；
6th, it is 5mm in roll spacing by sizing material, by three times on the open mill that roller temperature is 50 DEG C；Batch mixing glue parks 4h；
7th, banbury rotating speed is adjusted to 60rpm, temperature is 40 DEG C, and the batch mixing glue that step 6 is obtained adds mixer mixing
Vulcanizing agent and vulcanization accelerator, glue stuff compounding, when sizing material temperature reaches 110 DEG C and keeps at such a temperature are added after 30s
During 4min, sizing material is unloaded；
8th, it is 0.5mm in roll spacing by the batch mixing glue that step 7 obtains, by once on the open mill that roller temperature is 50 DEG C, then
Roll spacing is adjusted to 3mm, then by twice；Rubber compound parks 24h；
9th, the sizing material for obtaining step 8 is vulcanized, wherein, curing temperature is 160 DEG C, pressure 15MPa, vulcanization time
The sulfurizing time t measured according to no rotor vulcameterc90It is determined as 30min.
As a result vulcanization rubber DS1 is obtained.
Comparative example 2：The method for preparing vulcanization rubber DS2
This comparative example is carried out using method similar to Example 2, the difference is that the white carbon combination in this comparative example
Thing is a feed postition, specifically：
1st, at 70 DEG C, white carbon, silane coupling agent and stearic acid are mixed into 5min in high-speed mixer, then in height
5 each 8s are ground in fast grinder, obtain white carbon composition, white carbon composition is kept the temperature using preceding in 120 DEG C of baking ovens
3h；Carbon black keeps the temperature 2h in 110 DEG C of baking ovens before use；
2nd, 1/4 solution polymerized butadiene styrene rubber for accounting for whole solution polymerized butadiene styrene rubber weight is added into mixer the 0.4min that plasticates,
Wherein, banbury rotating speed 90rpm, initial temperature of plasticating are 85 DEG C；
3rd, white carbon composition and whole softening agent that step 1 obtains are added in mixer and is kneaded 2min, control mixing
Temperature in machine is no more than 140 DEG C；Sizing material is unloaded, roller is crossed in two-roll mill and cuts out block, obtains the second rubber compound；
4th, remainder solution polymerized butadiene styrene rubber is added into mixer the 0.4min that plasticates, banbury rotating speed 90rpm, mixing
Initial temperature is 85 DEG C；Second rubber compound is added in mixer and controls temperature in mixer to be no more than 140 DEG C of mixings
2min；
5th, carbon black, antioxidant and zinc oxide are added in mixer and is kneaded, kept when mixing temperature reaches 160 DEG C
5min, then unloads sizing material；
6th, it is 5mm in roll spacing by sizing material, by three times on the open mill that roller temperature is 50 DEG C；Batch mixing glue parks 4h；
7th, banbury rotating speed is adjusted to 60rpm, temperature is 40 DEG C, and the batch mixing glue that step 6 is obtained adds mixer mixing
Vulcanizing agent and vulcanization accelerator, glue stuff compounding, when sizing material temperature reaches 110 DEG C and keeps at such a temperature are added after 30s
During 4min, sizing material is unloaded；
8th, it is 0.5mm in roll spacing by the batch mixing glue that step 7 obtains, by once on the open mill that roller temperature is 50 DEG C, then
Roll spacing is adjusted to 3mm, then by twice；Rubber compound parks 24h；
9th, the sizing material for obtaining step 8 is vulcanized, wherein, curing temperature is 150 DEG C, pressure 14MPa, vulcanization time
The sulfurizing time t measured according to no rotor vulcameterc90It is determined as 30min.
As a result vulcanization rubber DS2 is obtained.
Comparative example 3：The method for preparing vulcanization rubber DS3
This comparative example is carried out using method similar to Example 3, the difference is that the main rubber in this comparative example is
Feed postition, specifically：
1st, at 60 DEG C, white carbon, silane coupling agent and stearic acid are mixed into 5min in high-speed mixer, then in height
4 each 10s are ground in fast grinder, obtain white carbon composition, white carbon composition is kept the temperature using preceding in 120 DEG C of baking ovens
3h；Carbon black keeps the temperature 2h in 100 DEG C of baking ovens before use；
2nd, whole solution polymerized butadiene styrene rubbers are added into mixer the 0.4min that plasticates, wherein, banbury rotating speed 90rpm, modeling
It is 75 DEG C to refine initial temperature；
3rd, the white carbon composition and whole softening agents obtained 5/8 step 1 for accounting for whole white carbon composition weights
Add in mixer and be kneaded 2min, control the temperature in mixer to be no more than 140 DEG C；Then the white carbon of remainder is combined
Thing is added in mixer, and controls the temperature in mixer to be kneaded 2min in the range of no more than 140 DEG C；Sizing material is unloaded, double
Roller is crossed on roller open mill and cuts out block, obtains the second rubber compound；
4th, it is 90rpm in banbury rotating speed, under the conditions of mixing initial temperature is 75 DEG C, second rubber compound is added close
In mill and temperature in mixer is controlled to be no more than 140 DEG C of mixing 2min；
5th, carbon black, antioxidant and zinc oxide are added in mixer and is kneaded, kept when mixing temperature reaches 160 DEG C
5min, then unloads sizing material；
6th, it is 5mm in roll spacing by sizing material, by three times on the open mill that roller temperature is 50 DEG C；Batch mixing glue parks 4h；
7th, banbury rotating speed is adjusted to 60rpm, temperature is 40 DEG C, and the batch mixing glue that step 6 is obtained adds mixer mixing
Vulcanizing agent and vulcanization accelerator, glue stuff compounding, when sizing material temperature reaches 110 DEG C and keeps at such a temperature are added after 30s
During 4min, sizing material is unloaded；
8th, it is 0.5mm in roll spacing by the batch mixing glue that step 7 obtains, by once on the open mill that roller temperature is 50 DEG C, then
Roll spacing is adjusted to 3mm, then by twice；Rubber compound parks 24h；
9th, the sizing material for obtaining step 8 is vulcanized, wherein, curing temperature is 170 DEG C, pressure 12MPa, vulcanization time
The sulfurizing time t measured according to no rotor vulcameterc90It is determined as 30min.
As a result vulcanization rubber DS3 is obtained.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| SSBR2636 | 137.5 | --- | 137.5 |
| SSBR2506 | --- | 100 | --- |
| TDAE | 0 | 37.5 | 0 |
| N115 | 10 | --- | --- |
| N234 | --- | --- | 8 |
| N330 | --- | 15 | --- |
| 165GR | 60 | --- | 65 |
| 1165MP | --- | 55 | --- |
| Sulphur | 0.5 | 1.5 | 2 |
| Diphenylguanidine PG | 2 | 1.5 | 1.5 |
| Accelerator TBBS | 0 | 1.5 | 2.5 |
| ZnO | 2 | 2 | 3 |
| SA | 2 | 3 | 4 |
| Si69 | 4 | 5 | --- |
| Si75 | --- | --- | 8 |
| Microwax | 1.5 | 1 | 1.5 |
| Anti-aging agent RD | --- | 2 | --- |
| Antioxidant MB | --- | --- | 4.5 |
| Antioxidant 4010 | 1.8 | --- | --- |
Test case
The performance of above-mentioned vulcanization rubber S1-S6, DS1-DS3 are tested according to preceding method, including：Mechanical property, dynamic force
Performance, dynamic compression heat build-up, DIN abrasion and resilience performance are learned, as a result as shown in table 2.
Table 2
From table 2 it can be seen that by the vulcanization rubber that the method for embodiment is prepared and the method acquisition by comparative example
Vulcanize rubber phase ratio, in terms of tensile strength, stress at definite elongation, tearing strength, compression heat generation and wear-resisting property, reality of the invention
It is more excellent to apply the above-mentioned performance of the vulcanization rubber of the method acquisition of example, there is excellent comprehensive physical performance.In dynamic mechanical
Energy aspect, the tan δ (0 DEG C) for the vulcanization rubber that method of the invention obtains are above the tan of the vulcanization rubber obtained in comparative example
δ (0 DEG C) value, the value of the tan δ (60 DEG C) for the vulcanization rubber that method of the invention obtains are below the vulcanization rubber obtained in comparative example
Tan δ (60 DEG C) value of glue, that is, the vulcanization rubber that the method for the present invention obtains shows good wet-sliding resistant performance and low rolling
Dynamic resistance.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (16)
1. a kind of method for preparing vulcanization rubber, this method include：
(1) by a part of white carbon composition and a part of main rubber optionally and softening agent carry out first be kneaded；Then
The first rubber compound obtained after first is kneaded carries out second with remainder white carbon composition and is kneaded, and obtains the second mixing
Glue, the white carbon composition are pre-mixed by white carbon, coupling agent and at least part activator and are obtained；
(2) remainder main rubber and second rubber compound are carried out the 3rd to be kneaded, obtains the 3rd rubber compound；
(3) by the 3rd rubber compound and carbon black and antioxidant optionally and with softening agent and/or remainder activator into
Row the 4th is kneaded, and obtains the 4th rubber compound；Then the 4th rubber compound is carried out the 5th with vulcanizing agent and vulcanization accelerator to mix
Refining, obtains the 5th rubber compound；
(4) the 5th rubber compound is vulcanized.
2. according to the method described in claim 1, wherein, a part of white carbon composition accounts for whole white carbon composition weights
2/10 to the 9/10 of amount；Preferably,
A part of white carbon composition accounts for 1/2 to the 3/4 of whole white carbon composition weights.
3. method according to claim 1 or 2, wherein, a part of main rubber accounts for whole main rubber weight
1/12 to 1/2；Preferably,
A part of main rubber accounts for 1/4 to the 1/3 of whole main rubber weight.
4. according to the method described in any one in claim 1-3, wherein, in step (1), described first is kneaded and described
Second condition being kneaded is identical or different, includes independently of one another：Temperature is 70-150 DEG C, time 1-8min.
5. according to the method described in any one in claim 1-4, wherein, in step (2), the described 3rd condition being kneaded
Including：Temperature is 70-150 DEG C, time 1-8min.
6. according to the method described in any one in claim 1-5, wherein, in step (3), the described 4th condition being kneaded
Including：Temperature is 150-170 DEG C, time 4-10min；Preferably,
In step (3), the described 5th condition being kneaded includes：Temperature is 40-110 DEG C, time 1-7min.
7. according to the method described in any one in claim 1-6, wherein, in step (4), the condition bag of the vulcanization
Include：Temperature is 150-170 DEG C, pressure 10-15MPa, time 10-50min.
8. according to the method described in claim 1, wherein, in step (1), activate white carbon, coupling agent and at least partly
The condition that agent is pre-mixed includes：Temperature is 5-100 DEG C, time 5-10min.
9. according to the method described in any one in claim 1-8, wherein, this method further comprises：In step (1) and step
Suddenly in (3), using before the main rubber, first by the main rubber be 75-85 DEG C in initial temperature at plasticate 0.4-
0.6min。
10. according to the method described in claim 1-9, wherein, relative to the main rubber of 100 parts by weight, the hard charcoal
Black dosage is 55-65 parts by weight, and the dosage of the carbon black is 5-15 parts by weight, and the dosage of the softening agent is 0-25 weight
Part, the dosage of the coupling agent is 4-8 parts by weight, and the dosage of the antioxidant is 3-11 parts by weight, the dosage of the vulcanizing agent
For 0.5-2 parts by weight, the dosage of the vulcanization accelerator is 2-5 parts by weight, and the dosage of the activator is 4-8 parts by weight.
11. according to the method described in any one in claim 1-10, wherein, the main rubber is butadiene-styrene rubber；It is preferred that
Ground, the butadiene-styrene rubber are solution polymerized butadiene styrene rubber and/or emulsion polymerized styrene butadiene rubber.
12. according to the method described in any one in claim 1-10, wherein, the iodine absorption value of the carbon black is not less than 80g/
Kg, average particulate diameter are 10-40 nanometers, specific surface area 80-140m2/g；Preferably,
The specific surface area of the white carbon is 100-200m2/ g, is preferably 115-200m2/g。
13. according to the method described in any one in claim 1-10, wherein, the softening agent is petroleum line softener, excellent
Elect aromatic naphtha and/or naphthenic oil as；Preferably,
The coupling agent is silane coupling agent, and preferably described silane coupling agent is double-[γ-(triethoxysilicane) propyl group]-four sulphur
At least one of compound, gamma-aminopropyl-triethoxy-silane and double-[γ-(triethoxysilicane) propyl group]-disulphide；It is excellent
Selection of land,
The antioxidant is selected from least one of microwax, amines antioxidants and quinoline type antioxidant；It is preferred that the antioxidant
For microwax and the mixture selected from least one of anti-aging agent RD, antioxidant MB and antioxidant 4010 material；It is highly preferred that
The microwax is 1 with the content weight ratio selected from least one of anti-aging agent RD, antioxidant MB and antioxidant 4010 material：
1.2-3；Preferably,
The vulcanizing agent is sulphur；Preferably,
The vulcanization accelerator is diphenylguanidine, the N- tert-butyl groups -2-[4-morpholinodithio base sulfenamide, 2,2'- diphenyl disulfides and thiophene
In azoles, the N- tert-butyl groups-bis- (2-[4-morpholinodithio) sulfenamide and N- cyclohexyl-bis- (2-mercaptobenzothiazoles) sulfenamide
It is at least one；Preferably,
The activator is at least one of zinc oxide, magnesia and stearic acid.
14. the vulcanization rubber being prepared as the method described in any one in claim 1-13.
15. the vulcanization rubber in claim 1-13 described in any one.
16. application of the vulcanization rubber in tire is prepared described in claims 14 or 15.
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| CN110435031A (en) * | 2019-07-29 | 2019-11-12 | 怡维怡橡胶研究院有限公司 | A kind of compounding rubber processing technology for improving hardness, increasing modulus, improving tear resistance |
| CN112847870A (en) * | 2021-01-14 | 2021-05-28 | 中策橡胶集团有限公司 | White carbon black-containing rubber composition and mixing method thereof |
| CN118222019A (en) * | 2024-03-11 | 2024-06-21 | 赛轮集团股份有限公司 | 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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| EP2311922A1 (en) * | 2008-07-11 | 2011-04-20 | Nissin Kogyo Co., Ltd. | Sealing member for piping material having excellent chlorine resistance, method for producing sealing member for piping material having excellent chlorine resistance, sealing member for piping material having excellent oil resistance, and piping material |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110435031A (en) * | 2019-07-29 | 2019-11-12 | 怡维怡橡胶研究院有限公司 | A kind of compounding rubber processing technology for improving hardness, increasing modulus, improving tear resistance |
| 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 |
| CN112847870A (en) * | 2021-01-14 | 2021-05-28 | 中策橡胶集团有限公司 | White carbon black-containing rubber composition and mixing method thereof |
| 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 |
| CN118222019A (en) * | 2024-03-11 | 2024-06-21 | 赛轮集团股份有限公司 | Zinc-free rubber composition, tread rubber, and preparation method and application thereof |
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