CN117511018A - Rubber processing aid, preparation method and application thereof, rubber composition and application thereof, vulcanized rubber and preparation method and application thereof - Google Patents
Rubber processing aid, preparation method and application thereof, rubber composition and application thereof, vulcanized rubber and preparation method and application thereof Download PDFInfo
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- CN117511018A CN117511018A CN202210892384.7A CN202210892384A CN117511018A CN 117511018 A CN117511018 A CN 117511018A CN 202210892384 A CN202210892384 A CN 202210892384A CN 117511018 A CN117511018 A CN 117511018A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 116
- 239000005060 rubber Substances 0.000 title claims abstract description 116
- 238000010057 rubber processing Methods 0.000 title claims abstract description 81
- 239000006057 Non-nutritive feed additive Substances 0.000 title claims abstract description 80
- 239000004636 vulcanized rubber Substances 0.000 title claims abstract description 76
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000006229 carbon black Substances 0.000 claims abstract description 84
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000000178 monomer Substances 0.000 claims abstract description 61
- 239000002253 acid Substances 0.000 claims abstract description 60
- 238000002156 mixing Methods 0.000 claims abstract description 52
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 43
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 abstract description 28
- 230000020169 heat generation Effects 0.000 abstract description 15
- 125000003396 thiol group Chemical class [H]S* 0.000 abstract description 10
- 235000019241 carbon black Nutrition 0.000 description 73
- 238000004073 vulcanization Methods 0.000 description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 14
- 239000011593 sulfur Substances 0.000 description 14
- 229910052717 sulfur Inorganic materials 0.000 description 14
- 230000003712 anti-aging effect Effects 0.000 description 12
- 229920006978 SSBR Polymers 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 239000005062 Polybutadiene Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000011056 performance test Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 229920001195 polyisoprene Polymers 0.000 description 7
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 6
- 239000013543 active substance Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- HNWAHFPYJHAAJE-UHFFFAOYSA-N n-tert-butyl-1,3-benzothiazole-2-sulfonamide Chemical compound C1=CC=C2SC(S(=O)(=O)NC(C)(C)C)=NC2=C1 HNWAHFPYJHAAJE-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 230000036316 preload Effects 0.000 description 6
- 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 5
- 235000021355 Stearic acid Nutrition 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000012763 reinforcing filler Substances 0.000 description 5
- 239000008117 stearic acid Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 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 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000010692 aromatic oil Substances 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 229920003049 isoprene rubber Polymers 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 2
- DTRIDVOOPAQEEL-UHFFFAOYSA-N 4-sulfanylbutanoic acid Chemical compound OC(=O)CCCS DTRIDVOOPAQEEL-UHFFFAOYSA-N 0.000 description 2
- 241000487918 Acacia argyrodendron Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LINSLUIHIHAFNA-OWOJBTEDSA-N (E)-3-sulfanylprop-2-enoic acid Chemical group OC(=O)\C=C\S LINSLUIHIHAFNA-OWOJBTEDSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 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 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 229920003212 trans-1,4-polyisoprene Polymers 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of rubber, and discloses a rubber processing aid, a preparation method and application thereof, a rubber composition and application thereof, vulcanized rubber and a preparation method and application thereof. The rubber processing aid comprises a mercapto acid monomer, solution polymerized styrene-butadiene rubber and white carbon black; the content of the mercapto acid monomer is 60-200 parts by weight and the content of the white carbon black is 20-66.7 parts by weight relative to 100 parts by weight of the solution polymerized styrene-butadiene rubber. The rubber processing aid comprises a mercapto acid monomer, solution polymerized styrene-butadiene rubber and white carbon black, and is prepared by mixing the mercapto acid monomer, the solution polymerized styrene-butadiene rubber and the white carbon black in advance, so that the compatibility and the dispersibility of the mercapto acid monomer and a rubber matrix can be obviously improved, and the strength, the wear resistance and the wet skid resistance of the vulcanized rubber can be obviously improved on the premise of ensuring that the vulcanized rubber has low heat generation.
Description
Technical Field
The invention relates to the field of rubber, in particular to a rubber processing aid, a preparation method and application thereof, a rubber composition and application thereof, vulcanized rubber and a preparation method and application thereof.
Background
In recent years, the dynamic hysteresis loss performance of green tires determines the classification of the tires, and also causes the reduction of the strength and wear resistance of the rubber, causing early damage to the tires, and also increases the rolling resistance of the tires, and increases the fuel consumption and the carbon dioxide emission.
CN102382338A discloses an isoprene rubber blend comprising isoprene rubber, trans-1, 4-polyisoprene, reinforcing filler, in situ graft modification aid, compounded rubber and a first additive. The in-situ grafting modification auxiliary agent adopted in the prior art is subjected to grafting reaction with functional groups such as double bonds on a rubber molecular chain while undergoing chemical reaction with the reinforcing filler, so that the interfacial binding force between an organic polymer and the reinforcing filler and the dispersion level of the reinforcing filler in rubber are greatly improved, and the fatigue resistance of the isoprene rubber blend is improved.
CN103881161a discloses a trans-polyisoprene rubber and cis-polyisoprene rubber composition and processing technology thereof, and specifically discloses a rubber composition, wherein the total amount of synthetic trans-polyisoprene and synthetic cis-polyisoprene is 5-60 parts by mass, 40-95 parts by mass of natural rubber, 5-90 parts by mass of white carbon black and 5-90 parts by mass of carbon black, based on 100 parts by mass of rubber; the masterbatch process comprises the following steps: mixing the synthetic trans-polyisoprene or the composition of the synthetic trans-polyisoprene and the synthetic cis-polyisoprene rubber with white carbon black and a coupling agent to obtain white carbon black wood gum; mixing natural rubber and carbon black to obtain carbon black master batch; and (3) final rubber mixing process: and mixing the carbon black master batch, the white carbon black wood gum, the anti-aging agent, the active agent, the accelerator and the vulcanizing agent to prepare the rubber composition. The rubber compound prepared by the rubber composition and the process in the prior art has the characteristics of improving wear resistance and reducing heat generation, and can be applied to rubber products, particularly automobile tires, and can reduce rolling resistance and heat generation.
CN103703072a discloses a rubber composition for a tread, which contains a solution polymerized styrene-butadiene rubber, carbon black, silica and polyethylene glycol, wherein the content of the solution polymerized styrene-butadiene rubber in 100 mass% of the rubber component is 60 mass% or more, the content of the carbon black is 10 mass parts or less, the content of the silica is 50 mass parts or more, and the content of the polyethylene glycol is 0.1 to 3.5 mass parts with respect to 100 mass parts of the rubber component. According to this prior art, a rubber composition containing solution polymerized styrene-butadiene rubber, carbon black, silica and polyethylene glycol in prescribed amounts, respectively, can provide a pneumatic tire with improved fuel economy and wear resistance in balance when applied to a tire tread. In addition, the vulcanization speed is good when the tire is manufactured, and the appearance of the manufactured tire is good.
CN103087365a discloses a rubber composition for a wet skid and wear resistant balance tire tread, comprising a diene elastomer, an inorganic reinforcing filler, a coupling agent and a plasticizer. In this prior art, when a tire comprising a rubber composition is used, the tread of the tire has excellent wet skid resistance, gives the tire a balance of properties of wet grip and wear resistance, and is used for manufacturing a semi-steel radial car tire.
However, the rubber provided by the prior art still cannot meet the requirements of strength, heat generation reduction and wet skid performance improvement of the tread rubber of the tire, and there is a need for providing a rubber with improved performance.
CN107964138A discloses an application of a mercapto acid monomer and an application thereof in tire tread, in which the mercapto acid monomer and a rubber matrix are mixed in the prior art, so that the bridge effect of the matrix modifier mercapto acid monomer in the matrix rubber and white carbon black can be better exerted, the interaction of the white carbon black and the rubber matrix is facilitated, the strength of vulcanized rubber prepared by further vulcanization can be better improved, the heat generation of the vulcanized rubber is reduced, and the wet skid resistance of the vulcanized rubber sizing material is improved. However, the mercapto acid monomer has the disadvantages of bad smell, poor compatibility with a high-viscosity rubber matrix, poor dispersibility, inaccurate feeding and the like, so that the application of the mercapto acid monomer is limited to a certain extent.
Disclosure of Invention
The invention aims to overcome the defects that the compatibility and the dispersibility of a mercapto acid monomer in a high-viscosity rubber matrix are poor in the prior art, and the gel content of the matrix is high due to the high concentration of the local mercapto acid monomer in the in-situ modification process by using the mercapto acid monomer, so that the strength, the wear resistance, the wet skid resistance, the heat generation and the like of vulcanized rubber are affected. The rubber processing aid comprises a mercapto acid monomer, solution polymerized styrene-butadiene rubber and white carbon black, and the mercapto acid monomer, the solution polymerized styrene-butadiene rubber and the white carbon black are mixed in advance to prepare the rubber processing aid, so that the compatibility and dispersibility of the mercapto acid monomer and a rubber matrix can be remarkably improved, and the strength, wear resistance and wet skid resistance of the vulcanized rubber can be remarkably improved on the premise of ensuring that the vulcanized rubber has low heat generation.
In order to achieve the above object, a first aspect of the present invention provides a rubber processing aid, characterized in that the rubber processing aid comprises a mercapto acid monomer, a solution polymerized styrene-butadiene rubber, and white carbon black;
the content of the mercapto acid monomer is 60-200 parts by weight and the content of the white carbon black is 20-66.7 parts by weight relative to 100 parts by weight of the solution polymerized styrene-butadiene rubber.
The second aspect of the invention provides a method for preparing a rubber processing aid, which is characterized by comprising the following steps:
(1) Stirring white carbon black and a mercapto acid monomer until the white carbon black and the mercapto acid monomer are uniformly mixed to obtain a pre-loaded mixture;
(2) Plasticating the solution polymerized styrene-butadiene rubber to obtain plasticated rubber;
(3) Mixing the pre-loaded mixture with the plasticated rubber to obtain the rubber processing aid;
wherein the content of the mercapto acid monomer is 60-200 parts by weight and the content of the white carbon black is 20-66.7 parts by weight relative to 100 parts by weight of the solution polymerized styrene-butadiene rubber.
In a third aspect, the present invention provides a rubber processing aid prepared by the above-described preparation method.
In a fourth aspect, the present invention provides the use of the rubber processing aid described above in the preparation of vulcanized rubber.
A fifth aspect of the present invention provides a rubber composition characterized in that the rubber composition comprises the above-mentioned rubber processing aid and a base rubber;
wherein the rubber processing aid is used in an amount of 0.2 to 4 parts by weight, preferably 0.5 to 2 parts by weight, relative to 100 parts by weight of the base rubber.
In a sixth aspect, the present invention provides a method for producing a vulcanized rubber, comprising:
mixing all components in a rubber composition containing a rubber processing aid and base rubber to obtain a rubber compound blank, and vulcanizing the rubber compound blank to obtain vulcanized rubber;
wherein the rubber processing aid is the rubber processing aid.
The seventh aspect of the present invention provides a vulcanized rubber produced by the above-described production method.
An eighth aspect of the present invention provides the use of the above rubber composition or vulcanized rubber in a tread of a tire.
Through the technical scheme, the rubber processing aid, the preparation method and the application thereof, the rubber composition and the application thereof, the vulcanized rubber, the preparation method and the application thereof have the following beneficial effects:
the rubber processing aid provided by the invention comprises the mercapto acid monomer, the solution polymerized styrene-butadiene rubber and the white carbon black, and the mercapto acid monomer, the matrix material and the white carbon black are mixed in advance to prepare the rubber processing aid, so that the compatibility and the dispersibility of the mercapto acid monomer and a rubber matrix can be obviously improved, and the strength, the wear resistance and the wet skid resistance of the vulcanized rubber can be obviously improved on the premise of ensuring that the vulcanized rubber has low heat generation. When the vulcanized rubber is used for a tire tread, the durability of the tire and the safety of an automobile can be remarkably improved.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a rubber processing aid, which is characterized in that the rubber processing aid comprises a mercapto acid monomer, solution polymerized styrene-butadiene rubber and white carbon black;
the content of the mercapto acid monomer is 60-200 parts by weight and the content of the white carbon black is 20-66.7 parts by weight relative to 100 parts by weight of the solution polymerized styrene-butadiene rubber.
The rubber processing aid provided by the invention comprises the mercapto acid monomer, the solution polymerized styrene-butadiene rubber and the white carbon black, and the mercapto acid monomer, the matrix material and the white carbon black are mixed in advance to prepare the rubber processing aid, so that the compatibility and the dispersibility of the mercapto acid monomer and a rubber matrix can be obviously improved, and the strength, the wear resistance and the wet skid resistance of the vulcanized rubber can be obviously improved on the premise of ensuring that the vulcanized rubber has low heat generation. When the vulcanized rubber is used for a tire tread, the durability and safety of an automobile can be remarkably improved.
Furthermore, the sulfhydryl acid monomer is matched with the rubber matrix through the rubber processing aid provided by the invention, so that the pungent odor generated by the sulfhydryl acid monomer is reduced, the rubber processing aid is environment-friendly, more importantly, the weighing is convenient, the feeding is accurate, and the batch quality stability is improved.
Further, when the amounts of the mercapto acid monomer, the solution polymerized styrene-butadiene rubber and the white carbon black satisfy the above ranges, the loading amount of the mercapto acid monomer of the modifier can be increased, the pungent odor generated when the mercapto acid monomer is added in situ can be reduced, the weighing in the preparation process is convenient and accurate, and the dispersibility of the rubber processing aid in the rubber matrix is remarkably improved.
According to the present invention, the mercapto acid monomer is contained in an amount of 89 to 143 parts by weight and the white carbon black is contained in an amount of 27 to 46 parts by weight relative to 100 parts by weight of the solution polymerized styrene-butadiene rubber.
According to the present invention, the mercapto acid-based monomer is provided by at least one of compounds represented by formula (1):
wherein x is 0 and R 2 is-SH; or,
x is 1, M is a structure represented by formula (2), R 1 And R is 2 Each independently is H or-SH, and R 1 And R is 2 Not simultaneously H; or,
x is 2, M is a structure represented by formula (2), R 2 R in 2M 1 Each independently is H or-SH, and R 2 R in two M 1 Not simultaneously H; or,
x is 3, M is a structure represented by formula (2), R 2 R in 3M 1 Each independently is H or-SH, and R 2 R in 3M 1 And not H at the same time.
In the invention, the compound shown in the formula (1) is selected as the sulfhydryl acid monomer, and the rubber processing aid containing the sulfhydryl acid monomer is added into the rubber matrix, so that the dispersibility and compatibility among the matrix rubber, the white carbon black and the sulfhydryl acid monomer can be obviously improved, and the strength, the wear resistance and the wet skid resistance of the vulcanized rubber can be obviously improved on the premise of ensuring that the vulcanized rubber has low heat generation, and the vulcanized rubber is suitable for being used as tire tread rubber.
In one embodiment of the present invention, the mercapto-acid based monomer is 3-mercapto-acrylic acid and/or 4-mercapto-butyric acid.
According to the invention, in the solution polymerized styrene-butadiene rubber, the content of the styrene structural unit is 10-30wt% and the content of the vinyl is 40-70wt%.
Further, in the solution polymerized styrene-butadiene rubber, the content of the styrene structural unit is 20-25wt% and the content of the vinyl is 55-65wt%.
According to the present invention, the solution polymerized styrene-butadiene rubber has a Mooney viscosity (100 ℃, 1+4min) of 55 to 75, preferably 60 to 65.
In the present invention, the type of the white carbon black is not particularly limited, and may be a white carbon black of a conventional type in the art, for example, a vapor phase white carbon black and/or a precipitation white carbon black, and preferably the white carbon black is a precipitation white carbon black.
The second aspect of the invention provides a method for preparing a rubber processing aid, which is characterized by comprising the following steps:
(1) Stirring white carbon black and a mercapto acid monomer until the white carbon black and the mercapto acid monomer are uniformly mixed to obtain a pre-loaded mixture;
(2) Plasticating the solution polymerized styrene-butadiene rubber to obtain plasticated rubber;
(3) Mixing the pre-loaded mixture with the plasticated rubber to obtain the rubber processing aid;
wherein the content of the mercapto acid monomer is 60-200 parts by weight and the content of the white carbon black is 20-66.7 parts by weight relative to 100 parts by weight of the solution polymerized styrene-butadiene rubber.
According to the invention, the rubber processing aid agent disclosed by the first aspect is obtained by mixing white carbon black and a mercapto acid monomer and then mixing the mixture with plasticated rubber of solution polymerized styrene-butadiene rubber, so that the mercapto acid monomer, the white carbon black and a matrix material are fully and uniformly mixed in advance, the compatibility and dispersibility of the mercapto acid monomer and the rubber matrix are obviously improved, and when the rubber processing aid agent is used for preparing vulcanized rubber, the strength, the wear resistance and the wet skid resistance of the vulcanized rubber are obviously improved on the premise of ensuring that the vulcanized rubber has low heat generation.
The amount and kind of raw materials for preparing the rubber processing aid according to the second aspect of the present invention are exactly the same as those described in the first aspect of the present invention, and the present invention is not repeated in this second aspect, and those skilled in the art should not understand the limitation of the present invention.
In the present invention, the mixing mode of the white carbon black and the mercapto acid monomer is not particularly limited as long as a uniform pre-load mixture of the white carbon black and the mercapto acid monomer can be formed.
According to the invention, the plasticating conditions include: the plasticating temperature is 20-40 ℃, the rotating speed is 30-60rpm, and the plasticating time is 1-2min.
In the invention, under the condition, the solution polymerized styrene-butadiene rubber is plasticated, so that the processing performance of the solution polymerized styrene-butadiene rubber can be improved, the solution polymerized styrene-butadiene rubber, the mercapto acid monomer and the white carbon black are uniformly mixed, and the compatibility and the dispersibility among the mercapto acid monomer, the matrix material and the white carbon black in the rubber processing aid are further improved.
In the present invention, the plastication may be carried out in conventional equipment in the art, preferably an internal mixer.
According to the invention, the mixing conditions include: the mixing time is 3-6min, and the mixing temperature is 60-90 ℃.
In the invention, the plasticated rubber and the pre-loaded mixture are mixed under the conditions, so that the plasticated rubber and the pre-loaded mixture are fully and uniformly mixed, and the prepared rubber processing aid has excellent dispersibility and compatibility among the components.
Further, the mixing conditions include: the mixing time is 3-6min, and the mixing temperature is 60-70 ℃.
In the present invention, the mixing may be carried out in conventional equipment in the art, preferably an internal mixer.
In a third aspect, the present invention provides a rubber processing aid prepared by the above-described preparation method.
In a fourth aspect, the present invention provides the use of the rubber processing aid described above in the preparation of vulcanized rubber.
A fifth aspect of the present invention provides a rubber composition characterized in that the rubber composition comprises the above-mentioned rubber processing aid and a base rubber;
wherein the rubber processing aid is used in an amount of 0.2 to 4 parts by weight relative to 100 parts by weight of the base rubber.
Further, the rubber processing aid is used in an amount of 0.5 to 2 parts by weight relative to 100 parts by weight of the base rubber.
In the present invention, the base rubber may be any of various rubbers conventionally used in the art that require vulcanization processing, and may include, but is not limited to: natural rubber and/or synthetic rubber, which may include, but is not limited to: butadiene rubber and/or styrene-butadiene rubber.
In the present invention, additives conventional in the art, such as white carbon black, an active agent, an anti-aging agent, a vulcanizing agent, an accelerator, and the like, are also included in the rubber composition.
In the present invention, the white carbon black may be any of various existing precipitation method white carbon blacks which can be used for reinforcing rubber, and may include, but is not limited to: white carbon black 200MP, 1165MP, 165GR and 115GR, wherein the content of the white carbon black can be selected in a larger range; specifically, the content of the white carbon black may be 40 to 100 parts by weight with respect to 100 parts by weight of the base rubber.
In the present invention, the carbon black may be any of a variety of existing carbon blacks that can be used as rubber additives, including but not limited to: carbon blacks N550, N774 and N330, the content of the carbon black may be selected in a wide range; specifically, the carbon black may be contained in an amount of 0 to 70 parts by weight relative to 100 parts by weight of the base rubber.
The type and amount of the active agent is also well known to those skilled in the art, and the active agent may be zinc oxide and/or stearic acid; specifically, the content of the active agent may be 2 to 10 parts by weight with respect to 100 parts by weight of the natural rubber and the synthetic rubber.
In the invention, the softener is at least one of aromatic oil, paraffin oil, naphthenic oil, petroleum resin and polyethylene glycol. Wherein the weight average molecular weight of the polyethylene glycol is 3000-5000, so that the composite material has better processing performance and physical and mechanical properties. The aromatic oil may be, for example, aromatic oil TDAE V500, and the polyethylene glycol may be, for example, polyethylene glycol PEG4000. Specifically, the softener may be contained in an amount of 5 to 15 parts by weight with respect to 100 parts by weight of the base rubber.
In the invention, the anti-aging agent is at least one of amine anti-aging agent, quinoline anti-aging agent and benzimidazole anti-aging agent. For example, the anti-aging agent is anti-aging agent 4020. Specifically, the content of the antioxidant may be 1 to 5 parts by weight with respect to 100 parts by weight of the base rubber.
In the present invention, the accelerator is at least one of a sulfenamide accelerator, a thiazole accelerator, a thiuram accelerator and a guanidine accelerator. The accelerator may be N-tert-butyl-2-benzothiazole sulfonamide (TBBS), diphenylguanidine (accelerator D). Specifically, the accelerator may be contained in an amount of 0.5 to 2.5 parts by weight relative to 100 parts by weight of the base rubber.
In the present invention, the vulcanizing agent is sulfur and/or a sulfur donor. The sulfur donor is a substance capable of providing sulfur. The sulfur comprises at least one of insoluble sulfur, soluble sulfur and oil-filled sulfur. For example, the vulcanizing agent IS ordinary sulfur S, oil-filled insoluble sulfur IS, and the like. Specifically, the vulcanizing agent may be contained in an amount of 0.5 to 2.5 parts by weight relative to 100 parts by weight of the base rubber.
In a sixth aspect, the present invention provides a method for producing a vulcanized rubber, comprising:
mixing all components in a rubber composition containing a rubber processing aid and base rubber to obtain a rubber compound blank, and vulcanizing the rubber compound blank to obtain vulcanized rubber;
wherein the rubber processing aid is the rubber processing aid.
In the invention, each component in the rubber composition is mixed in the presence of the rubber processing aid provided in the first aspect or the third aspect of the invention to obtain a rubber compound blank, and the rubber compound blank is vulcanized, so that the dispersibility and compatibility of the mercapto acid monomer in the rubber processing aid in the base rubber can be obviously improved, and the strength, the wear resistance and the wet skid resistance of the vulcanized rubber can be further improved on the premise that the produced vulcanized rubber has low heat generation.
In the present invention, the specific process and operation of mixing the components in the rubber composition and curing the compound can be carried out with reference to the prior art. Specifically, the vulcanized rubber is prepared according to the following method:
s1, carrying out first mixing on base rubber and a rubber processing aid to obtain first mixed rubber; wherein the conditions of the first kneading include: the mixing time is 1-5min, and the mixing temperature is 60-100 ℃;
s2, carrying out second mixing on the first mixed rubber, white carbon black, an active agent, a softening agent and an anti-aging agent to obtain a second mixed rubber, wherein the second mixing conditions comprise: the mixing time is 5-10min, and the mixing temperature is 80-160 ℃;
s3, standing the second rubber compound, and then carrying out third mixing with a vulcanizing agent and an accelerator to obtain a rubber compound blank, wherein the standing conditions comprise: standing for more than 4 hours at room temperature; the conditions for the third kneading include: the mixing time is 3-7min, and the mixing temperature is not more than 130 ℃;
s4, vulcanizing the rubber compound blank to obtain tire tread rubber, wherein the vulcanization conditions comprise: the vulcanization temperature is 140-170 ℃, the vulcanization time is 30-40min, and the vulcanization pressure is 10-20MPa.
In the present invention, the first mixing, the second mixing, and the third mixing may be performed in mixing equipment conventional in the art, such as an internal mixer.
In the present invention, the vulcanization may be carried out in a vulcanization apparatus conventional in the art, such as a press vulcanizer.
The seventh aspect of the present invention provides a vulcanized rubber produced by the above-described production method.
An eighth aspect of the present invention provides the use of the above rubber composition or vulcanized rubber in a tread of a tire.
The present invention will be described in detail by examples.
The equipment conditions for preparing vulcanized rubber in the following examples and comparative examples are shown in Table 1.
The test instruments and test conditions of the vulcanized rubbers obtained in examples and comparative examples are shown in Table 2 and Table 3.
The amounts of the components in the following examples and comparative examples were each 1g per part by weight.
TABLE 1
| Sequence number | Device name | Model number | Manufacturing factories |
| 1 | Banbury mixer | BR1600 | America Rayleigh Corp |
| 2 | Flat vulcanizing machine | XLB-D400*400*2 | First rubber machinery plant of Shanghai |
TABLE 2
| Sequence number | Test item | Model of test instrument | Manufacturing factories |
| 1 | Tensile Strength | Universal pulling machine, SHIMADZU, AG-20KNG | Shimadzu corporation of Japan |
| 2 | DIN abrasion | GT-7012-A | High-speed rail detection instruments Co Ltd |
| 3 | Dynamic viscoelastometer | EPLEXOR 500N | German Gaobao Co Ltd |
| 4 | Rubber processing analyzer | RPA2000 | Alpha Co Ltd |
| 5 | Dynamic compression fatigue heat generation | Compression heat generation experimental machine Y3000E | Beijing friend deep electronic instruments Co., ltd |
TABLE 3 Table 3
Preparation examples 1 to 6 are provided for illustrating the rubber processing aid of the present invention and the preparation method thereof.
Preparation example 1
Uniformly stirring 12 parts by weight of precipitation white carbon black (1165 MP) and 40 parts by weight of 3-mercaptopropionic acid at room temperature (25 ℃) to obtain a pre-load mixture; setting an internal mixer at 20 ℃ and rotating at 60rpm, and putting 45 parts by weight of SSBR (styrene structural unit content 10wt%, vinyl content 40wt% and Mooney viscosity 55) into the internal mixer for plasticating for 1min; then adding the pre-loaded mixture into an internal mixer, and mixing with the plasticated matrix for 6min; and discharging to obtain the rubber processing aid X1.
Preparation example 2
Uniformly stirring 14 parts by weight of precipitation white carbon black (165 GR) and 45 parts by weight of 4-mercaptobutyric acid at room temperature (25 ℃) to obtain a pre-loaded mixture; setting an internal mixer at 30 ℃ and rotating at 45rpm, and putting 40 parts by weight of SSBR (styrene structural unit content of 20wt%, vinyl content of 70wt% and Mooney viscosity of 75) into the internal mixer for plasticating for 1.5min; then adding the pre-loaded mixture into an internal mixer, and mixing with the plasticated matrix for 4min; and discharging to obtain the rubber processing aid X2.
Preparation example 3
Uniformly stirring 16 parts by weight of precipitation white carbon black (1165 MP) and 50 parts by weight of 3-mercaptopropionic acid at room temperature (25 ℃) to obtain a pre-load mixture; setting an internal mixer at 40 ℃ and rotating at 30rpm, and putting 35 parts by weight of SSBR (styrene structural unit content of 30wt%, vinyl content of 55wt% and Mooney viscosity of 65) into the internal mixer for plasticating for 2min; then adding the pre-loaded mixture into an internal mixer, and mixing with the plasticated matrix for 3min; and discharging to obtain the rubber processing aid X3.
Preparation example 4
Uniformly stirring 20 parts by weight of precipitation-process white carbon black (1165 MP) and 60 parts by weight of 3-mercaptopropionic acid to obtain a pre-load mixture; setting an internal mixer at 40 ℃ and rotating at 30rpm, and putting 35 parts by weight of SSBR (styrene structural unit content of 30wt%, vinyl content of 55wt% and Mooney viscosity of 65) into the internal mixer for plasticating for 2min; then adding the pre-loaded mixture into an internal mixer, and mixing with the plasticated matrix for 3min; and discharging to obtain the rubber processing aid X4.
Preparation example 5
Uniformly stirring 10 parts by weight of precipitation-process white carbon black (1165 MP) and 55 parts by weight of 3-mercaptopropionic acid to obtain a pre-load mixture; setting an internal mixer at 40 ℃ and rotating at 30rpm, and putting 50 parts by weight of SSBR (styrene structural unit content of 30wt%, vinyl content of 55wt% and Mooney viscosity of 65) into the internal mixer for plasticating for 2min; then adding the pre-loaded mixture into an internal mixer, and mixing with the plasticated matrix for 3min; and discharging to obtain the rubber processing aid X5.
Preparation example 6
Uniformly stirring 30 parts by weight of precipitated white carbon black (1165 MP) and 70 parts by weight of 3-mercaptopropionic acid to obtain a pre-load mixture; setting an internal mixer at 40 ℃ and rotating at 30rpm, and putting 25 parts by weight of SSBR (styrene structural unit content of 30wt%, vinyl content of 55wt% and Mooney viscosity of 65) into the internal mixer for plasticating for 2min; then adding the pre-loaded mixture into an internal mixer, and mixing with the plasticated matrix for 3min; and discharging to obtain the rubber processing aid X6.
Examples 1-5 illustrate the vulcanized rubber provided by the present invention and a method for preparing the same.
Example 1
70 parts by weight of solution polymerized styrene-butadiene rubber (Yanshan petrochemical product, SSBR 2636) and 30 parts by weight of butadiene rubber (Yanshan petrochemical product, BR 9000) were added to an internal mixer together with 0.5 parts by weight of rubber processing aid X1, and mixed for 3 minutes at 70 ℃; then 60 parts by weight of white carbon black (165 GR, a company of rotunda, france), 15 parts by weight of carbon black (Ji Deli chemical engineering, N330, a company of doku city), 3 parts by weight of zinc oxide (a company of fang Hengfeng chemical, a company of doku constant), 2 parts by weight of stearic acid (a company of miku constant ), 10 parts by weight of aromatic hydrocarbon oil (a company of Santa Clara, TDAE V500), 3 parts by weight of an antioxidant (a company of Jiangsu san-o chemical, 4020) were added to an internal mixer to mix them, the mixture was allowed to stand at room temperature for 5 hours after the mixing was completed, then 2 parts by weight of sulfur (a company of Hengfu chemical, a company of Dongfu Co., ltd.) and 3 parts by weight of TBBS (N-t-butyl-2-benzothiazole sulfenamide) were added, and the obtained mixture was kneaded at 60 ℃ for 5 minutes to obtain a rubber compound, and then the obtained compound was subjected to press vulcanization at 160 ℃ under a vulcanization pressure of 10MPa and a vulcanization time of 40min, to obtain a vulcanized rubber sample S1.
The vulcanized rubber sample S1 was subjected to a performance test, and the results are shown in Table 4.
Example 2
70 parts by weight of solution polymerized styrene-butadiene rubber (Yanshan petrochemical product, SSBR 2636) and 30 parts by weight of butadiene rubber (Yanshan petrochemical product, BR 9000) were added to an internal mixer together with 1 part by weight of rubber processing aid X2, and mixed at 70℃for 3 minutes; then 60 parts by weight of white carbon black (165 GR, a company of rotunda, france), 15 parts by weight of carbon black (Ji Deli chemical engineering, N330, a company of doku city), 3 parts by weight of zinc oxide (a company of fang Hengfeng chemical, a company of doku constant), 2 parts by weight of stearic acid (a company of miku constant, a company of doku constant), 10 parts by weight of aromatic hydrocarbon oil (a company of Xinda (Ningbo), TDAE V500), 3 parts by weight of an anti-aging agent (a company of Jiangsu san chemical, 4020) were added to an internal mixer to mix them, and after mixing was completed, the mixture was left to stand at room temperature for 5 hours, then 2 parts by weight of sulfur (a company of Hengfang chemical, a company of doku constant), 3 parts by weight of TBBS (N-t-butyl-2-benzothiazole sulfenamide) were added, and then a rubber mix was obtained at 60 ℃ for 5 minutes, and then the obtained rubber mix was subjected to press vulcanization at 160 ℃ under a vulcanization pressure of 10MPa for 40 minutes, so as to obtain a vulcanized rubber sample S2.
The vulcanized rubber sample S2 was subjected to a performance test, and the results are shown in Table 4.
Example 3
70 parts by weight of solution polymerized styrene-butadiene rubber (Yanshan petrochemical product, SSBR 2636) and 30 parts by weight of butadiene rubber (Yanshan petrochemical product, BR 9000) were added to an internal mixer together with 2 parts by weight of rubber processing aid X3, and mixed for 3 minutes at 70 ℃; then 60 parts by weight of white carbon black (165 GR, french Rodi Co., ltd.), 15 parts by weight of carbon black (Ji Deli chemical technology Co., ltd., N330, dongguan Co., ltd.), 3 parts by weight of zinc oxide (Fabryo Hengfeng chemical Co., ltd.), 2 parts by weight of stearic acid (Fabryo Hengfeng chemical Co., ltd.), 10 parts by weight of aromatic hydrocarbon oil (Xindayang (Ningbo Co., ltd., TDAE V500), 3 parts by weight of an anti-aging agent (4020, st. O. Chemie Co., ltd.) were added to an internal mixer to mix, mixing for 7 minutes, standing to room temperature for 5 hours after mixing, adding 2 parts by weight of sulfur (constant chemical Co., ltd. In the building block) and 3 parts by weight of TBBS (N-tertiary butyl-2-benzothiazole sulfenamide), mixing for 5 minutes at 60 ℃ to obtain a rubber compound blank, and performing flat vulcanization on the obtained rubber compound blank, wherein the vulcanization temperature is 160 ℃, the vulcanization pressure is 10MPa, and the vulcanization time is 40 minutes, so as to obtain a vulcanized rubber sample S3.
The vulcanized rubber sample S3 was subjected to a performance test, and the results are shown in Table 4.
Example 4
70 parts by weight of solution polymerized styrene-butadiene rubber (Yanshan petrochemical product, SSBR 2636) and 30 parts by weight of butadiene rubber (Yanshan petrochemical product, BR 9000) were added to an internal mixer together with 3 parts by weight of rubber processing aid X4, and mixed for 3 minutes at 70 ℃; then 60 parts by weight of white carbon black (165 GR, french Rodi Co., ltd.), 15 parts by weight of carbon black (Ji Deli chemical technology Co., ltd., N330, dongguan Co., ltd.), 3 parts by weight of zinc oxide (Fabryo Hengfeng chemical Co., ltd.), 2 parts by weight of stearic acid (Fabryo Hengfeng chemical Co., ltd.), 10 parts by weight of aromatic hydrocarbon oil (Xindayang (Ningbo Co., ltd., TDAE V500), 3 parts by weight of an anti-aging agent (4020, st. O. Chemie Co., ltd.) were added to an internal mixer to mix, mixing for 7 minutes, standing to room temperature for 5 hours after mixing, adding 2 parts by weight of sulfur (constant chemical Co., ltd. In the building block) and 3 parts by weight of TBBS (N-tertiary butyl-2-benzothiazole sulfenamide), mixing for 5 minutes at 60 ℃ to obtain a rubber compound blank, and performing flat vulcanization on the obtained rubber compound blank, wherein the vulcanization temperature is 160 ℃, the vulcanization pressure is 10MPa, and the vulcanization time is 40 minutes, so as to obtain a vulcanized rubber sample S4.
The vulcanized rubber sample S4 was subjected to a performance test, and the results are shown in Table 4.
Example 5
A vulcanized rubber was prepared in the same manner as in example 1 except that 6 parts by weight of the rubber processing aid X5 was added to prepare a vulcanized rubber sample S5.
The vulcanized rubber sample S5 was subjected to a performance test, and the results are shown in Table 4.
Comparative example 1
A vulcanized rubber was prepared in the same manner as in example 1 except that the rubber processing aid X1 was added in an amount of 6 parts by weight to prepare a vulcanized rubber sample DS1.
The vulcanized rubber sample DS1 was subjected to a performance test, and the results are shown in Table 4.
Comparative example 2
A vulcanized rubber was prepared in the same manner as in example 1 except that the rubber processing aid X1 was replaced with the same added part of pure 3-mercaptopropionic acid (0.21 parts by weight) during the preparation of the vulcanized rubber, and vulcanized rubber DS2 was obtained.
The vulcanized rubber sample DS2 was subjected to a performance test, and the results are shown in Table 4.
Comparative example 3
A vulcanized rubber was prepared as in example 1, except that the rubber processing aid was added in an amount of 0.5 parts by weight of X6 to prepare a vulcanized rubber sample DS3.
The vulcanized rubber sample DS3 was subjected to a performance test, and the results are shown in Table 4.
Comparative example 4
A vulcanized rubber was prepared in the same manner as in example 1 except that no rubber processing aid was added during the preparation of the vulcanized rubber, and vulcanized rubber DS4 was obtained.
The vulcanized rubber sample DS4 was subjected to a performance test, and the results are shown in Table 4.
TABLE 4 Table 4
From the above results, the rubber processing aid provided by the invention can enable the white carbon black to have better dispersibility in the rubber matrix, and the interaction between the white carbon black and the rubber matrix is stronger, so that the strength of the vulcanized rubber can be better improved, the heat generation of the vulcanized rubber can be reduced, and the wet skid resistance can be improved.
Further, as can be seen from the data of comparative example 1 and comparative example 2, when the same rubber composition formulation as in example 1 is employed, but the mercapto-acidic monomer is added in a different manner, the further prepared vulcanized rubber DS2 is significantly inferior in performance to the vulcanized rubber S1, such as the tensile strength at break is lower than S1, the compression temperature rise is higher than S1, and the DIN abrasion is higher than S1; the dynamic mechanical properties of the vulcanizate of example 1 show less rolling resistance, better wet skid resistance, and the pecies effect data also demonstrate that the carbon black dispersion of the vulcanizate S1 of example 1 is significantly better than DS2.
The rubber processing aid and the preparation method can enable the obtained vulcanized rubber to have better performance, so that when the vulcanized rubber is applied to the tread of an automobile tire, the durability of the tire and the safety of the automobile can be improved.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (14)
1. A rubber processing aid, characterized in that the rubber processing aid comprises a mercapto acid monomer, solution polymerized styrene-butadiene rubber and white carbon black;
the content of the mercapto acid monomer is 60-200 parts by weight and the content of the white carbon black is 20-66.7 parts by weight relative to 100 parts by weight of the solution polymerized styrene-butadiene rubber.
2. The rubber processing aid according to claim 1, wherein the mercapto acid monomer is contained in an amount of 89 to 143 parts by weight and the white carbon black is contained in an amount of 27 to 46 parts by weight relative to 100 parts by weight of the solution polymerized styrene-butadiene rubber.
3. The rubber processing aid according to claim 1 or 2, wherein the mercapto acid-based monomer is provided by at least one of compounds represented by formula (1):
wherein x is 0 and R 2 is-SH; or,
x is 1, M is a structure represented by formula (2), R 1 And R is 2 Each independently is H or-SH, and R 1 And R is 2 Not simultaneously H; or,
x is 2, M is a structure represented by formula (2), R 2 R in 2M 1 Each independently is H or-SH, and R 2 R in two M 1 Not simultaneously H; or,
x is 3, M is a structure represented by formula (2), R 2 R in 3M 1 Each independently is H or-SH, and R 2 R in 3M 1 And not H at the same time.
4. The rubber processing aid according to any one of claims 1 to 3, wherein the solution polymerized styrene-butadiene rubber has a styrene structural unit content of 10 to 30wt% and a vinyl content of 40 to 70wt%;
preferably, the solution polymerized styrene-butadiene rubber has a Mooney viscosity of 55 to 75.
5. A method for preparing a rubber processing aid, the method comprising the steps of:
(1) Stirring white carbon black and a mercapto acid monomer until the white carbon black and the mercapto acid monomer are uniformly mixed to obtain a pre-loaded mixture;
(2) Plasticating the solution polymerized styrene-butadiene rubber to obtain plasticated rubber;
(3) Mixing the pre-loaded mixture with the plasticated rubber to obtain the rubber processing aid;
wherein the content of the mercapto acid monomer is 60-200 parts by weight and the content of the white carbon black is 20-66.7 parts by weight relative to 100 parts by weight of the solution polymerized styrene-butadiene rubber.
6. The preparation method according to claim 5, wherein the mercapto acid monomer is contained in an amount of 89 to 143 parts by weight and the white carbon black is contained in an amount of 27 to 46 parts by weight relative to 100 parts by weight of the solution polymerized styrene-butadiene rubber;
preferably, at least one of the compounds represented by the mercapto-acid monomer formula (1) provides:
wherein x is 0 and R 2 is-SH; or,
x is 1, M is a structure represented by formula (2), R 1 And R is 2 Each independently is H or-SH, and R 1 And R is 2 Not simultaneously H; or,
x is 2, M is a structure represented by formula (2), R 2 R in 2M 1 Each independently is H or-SH, and R 2 R in two M 1 Not simultaneously H; or,
x is 3, M is a structure represented by formula (2), R 2 R in 3M 1 Each independently is H or-SH, and R 2 R in 3M 1 And not H at the same time.
7. The production method according to claim 5 or 6, wherein the solution polymerized styrene-butadiene rubber has a styrene structural unit content of 10 to 25wt% and a vinyl content of 40 to 70wt%;
preferably, the solution polymerized styrene-butadiene rubber has a Mooney viscosity of 55 to 75.
8. The preparation method according to any one of claims 5 to 7, wherein the plasticating conditions include: the plasticating temperature is 20-40 ℃, the rotating speed is 30-60rpm, and the plasticating time is 1-2min;
preferably, the plastication is carried out in an internal mixer;
preferably, the mixing conditions include: the mixing time is 3-6min, and the mixing temperature is 60-90 ℃.
9. A rubber processing aid produced by the production method according to any one of claims 5 to 7.
10. Use of the rubber processing aid according to any one of claims 1 to 4 and 9 for the preparation of vulcanized rubber.
11. A rubber composition comprising the rubber processing aid of any one of claims 1 to 4 and 9 and a base rubber;
wherein the rubber processing aid is used in an amount of 0.2 to 4 parts by weight, preferably 0.5 to 2 parts by weight, relative to 100 parts by weight of the base rubber.
12. A method for producing a vulcanized rubber, characterized by comprising:
mixing all components in a rubber composition containing a rubber processing aid and base rubber to obtain a rubber compound blank, and vulcanizing the rubber compound blank to obtain vulcanized rubber;
wherein the rubber processing aid is the rubber processing aid agent according to any one of claims 1 to 4 and 9.
13. A vulcanized rubber produced by the production process of claim 12.
14. Use of the rubber composition of claim 11 or the vulcanized rubber of claim 13 in a tire tread.
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