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CN-121975202-A - Tread rubber composition reinforced by white carbon black improved by adopting functional oil and mixing method thereof

CN121975202ACN 121975202 ACN121975202 ACN 121975202ACN-121975202-A

Abstract

The invention relates to the technical field of tire rubber manufacturing, and discloses a tread rubber composition reinforced by white carbon black improved by adopting functional oil and a mixing method thereof. The tread rubber composition is added with an anchoring bio-based functional oil, the anchoring bio-based functional oil is polyether modified vegetable oil introduced with silane end groups, polyether chain segments are selected from Ethylene Oxide (EO) and Propylene Oxide (PO) polymers, and the silane end groups conform to a structural general formula- (CH 2 ) a —Z—(CH 2 ) b —Si(OR) 3 . The tread rubber composition can ensure rolling resistance and wear resistance, simultaneously remarkably improve processability (Mooney and ML) and white carbon black dispersion, expand mixing process window and improve batch-to-batch consistency, and has obvious industrial application value.

Inventors

  • WANG DANLING
  • LU XIAOQI
  • CHEN SHENG
  • HUANG DAYE
  • CHEN LI
  • LIU HUI

Assignees

  • 中策橡胶集团股份有限公司
  • 杭州海潮橡胶有限公司

Dates

Publication Date
20260505
Application Date
20260310

Claims (9)

  1. 1. The tread rubber composition reinforced by white carbon black is improved by adopting functional oil, and is characterized by being prepared by mixing the following raw materials in parts by weight: 100 parts by weight of a conjugated diene rubber, 50-120 Parts by weight of white carbon black, 1-12 Parts by weight of a silane coupling agent, 1-6 Parts by weight of an anchoring bio-based functional oil; The anchoring bio-based functional oil is polyether modified vegetable oil with silane end groups, wherein the polyether modified vegetable oil with silane end groups is characterized in that i) polyether chain segments are selected from EO and PO polymers, ii) 0.2-0.8 silane end groups are averagely introduced into each molecule, the silane end groups conform to the following structural general formula- (CH 2 ) a —Z—(CH 2 ) b —Si(OR) 3 , wherein R is C 1 –C 3 alkyl, a and b are 1-6, Z is-NH-CO-NH-, O-or-NH-, and iii) the number average molecular weight Mn is 1,000-5,000g/mol, and the bio-based carbon content is more than or equal to 60wt%; The anchoring bio-based functional oil meets the condition that the Hansen solubility three-parameter distance Ra_rubber of the Rubber phase is less than or equal to 6.0 (MPa 1 /2 ) and the Hansen solubility three-parameter distance Ra_Silica of the surface of the white carbon black is less than or equal to 8.0 (MPa 1/2 ).
  2. 2. The tread rubber composition reinforced by white carbon black improved by functional oil according to claim 1, wherein the rubber composition is prepared by mixing the raw materials comprising the following components in 100 parts by weight of raw rubber: 100 parts by weight of a conjugated diene rubber, 70-90 Parts by weight of white carbon black, 2-8 Parts by weight of a silane coupling agent, 1-6 Parts by weight of an anchoring bio-based functional oil, 1-5 Parts by weight of zinc oxide, 1-3 Parts by weight of stearic acid, Mineral oil 0-4 weight portions 1-3 Parts by weight of a vulcanizing agent, 1-5 Parts by weight of a promoter.
  3. 3. The tread rubber composition of claim 1 or 2, wherein the silane end groups are introduced by reaction of isocyanate-type silanes or epoxy/mercapto silanes with hydroxyl groups of polyether modified vegetable oils.
  4. 4. The tread rubber composition as claimed in claim 1 or 2, wherein Z is-NH-CO-NH-.
  5. 5. The tread rubber composition of claim 1 or 2, wherein the anchoring bio-based functional oil has a molar ratio of EO to PO of 20:80 to 80:20.
  6. 6. The tread rubber composition reinforced by white carbon black improved by functional oil according to claim 1 or 2, wherein the anchoring bio-based functional oil has a hydroxyl value of 10-80 mgKOH/g, an acid value of less than or equal to 3 mgKOH/g and an kinematic viscosity of 30-300 mm 2 /s at 100 ℃.
  7. 7. The tread rubber composition reinforced with white carbon black improved by a functional oil according to claim 1or2, wherein the white carbon black has a CTAB of 150 to 220 m 2 /g; And/or the silane coupling agent is selected from one or more of Si-69, si-75 and NXT, preferably, the mass ratio of the silane coupling agent to the anchoring bio-based functional oil is 1 (0.2-2); and/or the conjugated diene rubber is selected from one or more of solution polymerized styrene-butadiene rubber, butadiene rubber and natural rubber, preferably 55-65 parts by weight of solution polymerized styrene-butadiene rubber, 25-35 parts by weight of butadiene rubber and 5-15 parts by weight of natural rubber; and/or the mineral oil is selected from one or more of TDAE, NAP, MES, preferably, the mass ratio of the anchoring bio-based functional oil to the mineral oil is 1 (0-3).
  8. 8. A method of kneading a rubber composition according to any one of claims 1 to 7, comprising the steps of: 1) And (3) mixing: adding raw rubber, white carbon black, a silane coupling agent and other auxiliary materials (except for a vulcanizing agent, an accelerator and an anchoring bio-based functional oil), and mixing at 140-160 ℃ to obtain a first-stage mixing rubber; 2) Mixing in two stages, namely adding a first-stage mixed rubber and an anchoring bio-based functional oil, and continuously mixing for 1-4min at 140-160 ℃ and relative humidity of 0.1-0.5%, so as to obtain a second-stage mixed rubber; 2) And final mixing, namely adding the second-stage mixed rubber, carrying out thin-pass for 4-6 times at 55-65 ℃, and adding a vulcanizing agent and an accelerator, wherein the mixing temperature is less than 110 ℃ to obtain the final mixed rubber.
  9. 9. Tyre comprising a tread, sidewalls, a belt layer, characterized in that the tread of the tyre is obtained by vulcanization of a rubber composition according to any one of claims 1 to 7.

Description

Tread rubber composition reinforced by white carbon black improved by adopting functional oil and mixing method thereof Technical Field The invention relates to the technical field of tire rubber manufacturing, in particular to a tread rubber composition for improving white carbon black reinforcement by adopting functional oil and a mixing method thereof. Background In the rubber industry, especially in the field of tire manufacturing, white carbon black (silica) has become a key reinforcing filler for high-performance passenger tire treads and energy-saving rubber layers by virtue of the core advantages of the silica which can endow rubber with low rolling resistance and high wet grip performance. With the continuous upgrade of the global requirements on energy conservation and consumption reduction of automobiles and green environmental protection, the application ratio of the white carbon black in rubber products is increased year by year, but the high specific surface area (the CTAB specific surface area of the white carbon black for tires is more than 150-220m 2/g) of the white carbon black leads to the existence of a large number of silanol groups (Si-OH) on the surface, and the silanol groups are easy to form a compact particle-particle network through hydrogen bond interaction, thus causing the dual technical bottlenecks of low processing efficiency and difficult balance of performances, and becoming the core problem for restricting the industrial application of the white carbon black reinforced rubber system. From the aspect of processability dimension, the strong hydrogen bond network on the surface of the white carbon black significantly increases the dispersion resistance of the white carbon black in the rubber matrix. At the level of performance balance, the conventional solution always has difficulty in satisfying the dual requirements of "processability improvement" and "core performance retention". The prior art path is mainly divided into three types, namely, the chemical coupling of rubber and white carbon black is enhanced by increasing the dosage of a silane coupling agent, the interface bonding strength is improved, but the cost and performance imbalance are easily caused by simply relying on the silane coupling agent, secondly, mineral oil (such as TDAE oil, MES oil, NAP oil and the like) is adopted as a plasticizer, but the degree of entanglement of rubber molecular chains can be reduced only through physical filling of the mineral oil, the weakening of a white carbon black network is limited, thirdly, vegetable oil or a simple modifier thereof is adopted, the bio-based material has the advantages of green environmental protection, part of strong polar vegetable oil can improve initial wetting through interaction with silanol groups on the surface of the white carbon black, but the surface bonding sites of the white carbon black are easily preempted due to lack of accurate interface effect regulation. The modified biological base oil of the Chinese patent No. CN202211490295.6 is characterized in that the modified biological base oil of the Chinese patent No. CN202411922184.7 is characterized in that polysulfide bonds are introduced to participate in vulcanization, but the problem of 'plasticization-coupling' synergy is not solved. Therefore, there is an urgent need for a functional oil that combines "internal plasticization" with "interface control" to make it compatible with both rubber phase and form a moderate anchor with white carbon black, stabilizing processing window and viscoelastic properties. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a tread rubber composition reinforced by white carbon black by adopting functional oil and a mixing method thereof, which effectively improve the dispersion of the white carbon black and the processability of sizing materials. In order to achieve the above purpose, the present invention adopts the following technical scheme: The tread rubber composition reinforced by white carbon black is improved by adopting functional oil, and is prepared by mixing the following raw materials in parts by weight: 100 parts by weight of a conjugated diene rubber, 50-120 Parts by weight of white carbon black, 1-12 Parts by weight of a silane coupling agent, 1-6 Parts by weight of an anchoring bio-based functional oil; The anchoring bio-based functional oil is polyether modified vegetable oil with silane end groups, wherein the polyether modified vegetable oil with silane end groups is prepared by i) selecting polyether chain segments from Ethylene Oxide (EO) and Propylene Oxide (PO) polymers, ii) introducing 0.2-0.8 silane end groups per molecule, wherein the silane end groups conform to the following structural general formula- (CH 2)a—Z—(CH2)b—Si(OR)3), wherein R is C 1–C3 alkyl, a and b are 1-6, Z is-NH-CO-NH-, O-or-NH-, iii) the number average molecular weight Mn is 1,000-5,000g/mol, and the bio-based carbon conten