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CN-122011025-A - Synthesis method of bio-based dendritic phosphate derivative and application of bio-based dendritic phosphate derivative in tire tread rubber

CN122011025ACN 122011025 ACN122011025 ACN 122011025ACN-122011025-A

Abstract

The invention belongs to the technical field of rubber processing, and discloses a synthesis method of bio-based dendritic phosphate derivatives, which comprises the following specific steps of firstly, mixing ricinoleic acid and glycerin according to a molar ratio of 1:1.2 in an esterification reaction, adding 0.3% of p-toluenesulfonic acid as a catalyst, and reacting for 3 hours at 180 ℃ until the acid value of a reaction system is less than or equal to 5mgKOH/g, wherein the acid value of ricinoleic acid is more than or equal to 180mgKOH/g. The composition has high bio-based content, extremely low PAHs content and high biodegradation rate, meets strict environmental regulations from the source, has plasticizing, interface reinforcing and potential flame retarding functions on a single molecule, can effectively reduce the Mooney viscosity of rubber, improve the interface bonding strength of rubber and filler, can generate reversible dynamic crosslinking at high temperature and adapt to the dynamic working condition of a tire, and can obviously reduce the tan delta value of tread rubber at 60 ℃ and improve the tan delta value at 0 ℃ and reduce DIN abrasion in performance, thereby synergistically improving rolling resistance, wet skid performance and wear resistance.

Inventors

  • WANG FENG
  • TIAN ZHISHENG
  • LI YANGUO
  • XING TAO
  • QIU PEICHAO
  • XU JING
  • XU QINGFEI
  • LI DEHUI
  • YU JIALIN

Assignees

  • 山东玲珑轮胎股份有限公司

Dates

Publication Date
20260512
Application Date
20260114

Claims (9)

  1. 1. The synthesis method of the bio-based dendritic phosphate derivative is characterized by comprising the following specific steps: Step one, esterification reaction Mixing ricinoleic acid and glycerin according to a molar ratio of 1:1.2, adding 0.3% of p-toluenesulfonic acid as a catalyst, and reacting for 3 hours at 180 ℃ until the acid value of a reaction system is less than or equal to 5mgKOH/g, wherein the acid value of the ricinoleic acid is more than or equal to 180mgKOH/g; Step two, phosphorylation modification Adding to the product obtained in the step one Under the protection of nitrogen, the urea mixed reagent firstly heats the system to 85 ℃ and keeps the temperature for reaction for 2 hours, and the real-time monitoring is carried out through high performance liquid chromatography in the reaction process, so that the phosphorylation degree of the product is more than or equal to 92%; Step three, dendritic modification And (3) adding phosphorus oxychloride into the phosphorylated product obtained in the step (II), and reacting for 1.5 hours under the pressure of 0.1MPa and the temperature of 120 ℃ until the chloride ion content of the system is less than 0.1%, thereby preparing the bio-based dendritic phosphate derivative.
  2. 2. The method of synthesizing a biobased branched phosphate derivative according to claim 1, wherein the molecular structure of the biobased branched phosphate derivative in the third step is as follows: the core unit is glyceryl phosphate, the ratio of the bio-based raw materials in the glyceryl phosphate is more than or equal to 60%, and the branching structure comprises: a branch A is a C8-C12 alkyl chain which accounts for 35% -45% of the total weight of the biological basic branched phosphate derivative; A branch B, namely glycidyl ether groups accounting for 25% -35% of the total weight of the biological base branch phosphate derivative; A branch C, namely a phosphate group, accounting for 20% -30% of the total weight of the biological basic branched phosphate derivative; The molecular weight of the bio-based dendritic phosphate derivative is 800-1200 Da, the molecular weight distribution index PDI is less than or equal to 1.3, and the bio-based content is more than or equal to 85%.
  3. 3. The method of synthesizing a biobased branched phosphate derivative according to claim 1, wherein in the second step The mass ratio of the urea mixed reagent is 3:1, and the following components are adopted The urea mixed reagent can form stable phosphorylating active intermediate in the reaction system.
  4. 4. The method for synthesizing a biobased branched phosphate derivative according to claim 1, wherein in the second step, the reaction temperature is allowed to be within an error range of + -5 ℃ which is a reaction temperature range of 80 ℃ to 90 ℃ within which, The activity of the urea mixture reagent can be well matched with the reaction activity of the esterification product.
  5. 5. The method of claim 1, wherein the phosphorus oxychloride used in the third step is 1.1 times the theoretical amount of phosphorus oxychloride required for complete reaction with the hydroxyl group in the phosphorylated product obtained in the second step.
  6. 6. The application of the bio-based dendritic phosphate derivative prepared by the synthesis method according to the claims 1-5 in the tread rubber of the tire is characterized in that the bio-based dendritic phosphate derivative is used as operating oil to replace the traditional petroleum-based operating oil and is matched with rubber, filler and a vulcanization system in an application formula system to prepare the tread rubber of the tire by the following processes: one-stage mixing, namely mixing a rubber matrix with white carbon black at 140-150 ℃ for 4-6 minutes to obtain one-stage mixing rubber; Second-stage mixing, namely cooling the first-stage mixing rubber to 100-120 ℃, adding the bio-based dendritic phosphate derivative, the vulcanization system and other rubber additives, and mixing for 2-4 minutes; and (3) vulcanizing, namely calculating vulcanizing time according to the thickness of the rubber material at 153-157 ℃ and under the pressure of 1.2MPa for 1.5 minutes/millimeter, and naturally cooling to room temperature after vulcanizing to obtain the tire tread rubber.
  7. 7. The use of the bio-based branched phosphate derivative according to claim 6, wherein the specific surface area of the white carbon black is 180m2/g, and when the bio-based branched phosphate derivative is applied to a winter tire formulation, the bio-based branched phosphate derivative further comprises 5% of nano SiO 2 , the particle size is 25nm, the surface hydroxyl content is 3.8mmol/g, and the purity is 99.5% of the silane coupling agent Si-69.
  8. 8. The method for preparing the bio-based branched phosphate derivative according to claim 6, wherein the vulcanization treatment is carried out by a flat vulcanizing machine, the pressure fluctuation is kept to be not more than +/-0.05 MPa during the vulcanization, and the temperature deviation is controlled within +/-1 ℃.
  9. 9. The method of claim 6, wherein the bio-based branched phosphate derivative is used in the production of a tire tread rubber for a passenger or commercial vehicle.

Description

Synthesis method of bio-based dendritic phosphate derivative and application of bio-based dendritic phosphate derivative in tire tread rubber Technical Field The invention belongs to the technical field of rubber processing, in particular to a synthesis method of a bio-based dendritic phosphate derivative and application of the bio-based dendritic phosphate derivative in tire tread rubber. Background The bio-based dendritic phosphate derivative is a phosphate compound which is prepared by taking a bio-based raw material as a core and has a dendritic molecular topological structure. The invention discloses a modified trioctyl phosphate, which is characterized in that the modified trioctyl phosphate is used as a plasticizer or a flame retardant, for example, the patent with publication number CN119570128A, the PAHs content is reduced, the molecular structure is symmetrical, the bonding force with a rubber/filler interface is insufficient, the reinforcing effect is limited, the raw materials are mainly petroleum groups, the sustainable development trend is not met, the temperature responsiveness is lacked, the wide range of temperature variation in the running process of the tire is difficult to adapt, and the novel environment-friendly multifunctional V-shaped tire is difficult to adapt. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a synthesis method of a bio-based dendritic phosphate derivative and an application of the bio-based dendritic phosphate derivative in tire tread rubber, so as to solve the problems in the background art. In order to achieve the aim, the invention provides the following technical scheme that the synthesis method of the biological basic branched phosphate derivative comprises the following specific steps: Step one, esterification reaction Mixing ricinoleic acid and glycerin according to a molar ratio of 1:1.2, adding 0.3% of p-toluenesulfonic acid as a catalyst, and reacting for 3 hours at 180 ℃ until the acid value of a reaction system is less than or equal to 5mgKOH/g, wherein the acid value of the ricinoleic acid is more than or equal to 180mgKOH/g; Step two, phosphorylation modification Adding to the product obtained in the step oneUnder the protection of nitrogen, the urea mixed reagent firstly heats the system to 85 ℃ and keeps the temperature for reaction for 2 hours, and the real-time monitoring is carried out through high performance liquid chromatography in the reaction process, so that the phosphorylation degree of the product is more than or equal to 92%; Step three, dendritic modification And (3) adding phosphorus oxychloride into the phosphorylated product obtained in the step (II), and reacting for 1.5 hours under the pressure of 0.1MPa and the temperature of 120 ℃ until the chloride ion content of the system is less than 0.1%, thereby preparing the bio-based dendritic phosphate derivative. Preferably, the molecular structure of the biological basic branched phosphate derivative in the third step is as follows: the core unit is glyceryl phosphate, the ratio of the bio-based raw materials in the glyceryl phosphate is more than or equal to 60%, and the branching structure comprises: a branch A is a C8-C12 alkyl chain which accounts for 35% -45% of the total weight of the biological basic branched phosphate derivative; A branch B, namely glycidyl ether groups accounting for 25% -35% of the total weight of the biological base branch phosphate derivative; A branch C, namely a phosphate group, accounting for 20% -30% of the total weight of the biological basic branched phosphate derivative; The molecular weight of the bio-based dendritic phosphate derivative is 800-1200 Da, the molecular weight distribution index PDI is less than or equal to 1.3, and the bio-based content is more than or equal to 85%. Preferably, in step two, saidThe mass ratio of the urea mixed reagent is 3:1, and the following components are adoptedThe urea mixed reagent can form stable phosphorylating active intermediate in the reaction system. Preferably, the reaction temperature in the second step allows an error range of + -5 ℃, namely, the reaction temperature range is 80 ℃ to 90 ℃, and in the temperature range,The activity of the urea mixture reagent can be well matched with the reaction activity of the esterification product. Preferably, the phosphorus oxychloride used in the third step is 1.1 times of the theoretical value, and the theoretical value is the stoichiometric value of phosphorus oxychloride required for complete reaction with the hydroxyl group in the phosphorylated product obtained in the second step. The application of the bio-based dendritic phosphate derivative in the tire tread rubber is that the bio-based dendritic phosphate derivative is used as operating oil to replace traditional petroleum-based operating oil, and is matched with rubber, filler and a vulcanization system in an application formula system to prepare the tire tread rubber