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CN-122011539-A - Photo-thermal response self-repairing rubber sealing ring and preparation method and application thereof

CN122011539ACN 122011539 ACN122011539 ACN 122011539ACN-122011539-A

Abstract

The invention discloses a photo-thermal response self-repairing rubber sealing ring and a preparation method and application thereof, belonging to the technical field of rubber products, wherein the sealing ring comprises the following raw materials, by weight, 100 parts of a rubber base stock, 5-20 parts of double-wall microcapsules, 50-65 parts of a reinforcing component, 5-10 parts of a catalytic component, 2.5-3.5 parts of a vulcanizing agent, 2-3 parts of a cross-linking agent, 5-10 parts of a plasticizer, 1-2 parts of an antioxidant and 1-1.5 parts of an anti-aging agent; according to the invention, double-wall microcapsules and catalytic components are introduced into the sealing ring raw materials, so that a photo-thermal triggering-releasing-polymerization repairing three-in-one mechanism is realized, and the photo-thermal response self-repairing type rubber sealing ring can automatically repair internal damage caused by fatigue, abrasion or tiny puncture under the irradiation of external near infrared light (NIR), thereby recovering the sealing performance and remarkably prolonging the service life.

Inventors

  • WU XIAOBO
  • Miao jinchuan
  • CHEN ZHENGXIN
  • ZHANG YANQING
  • LI JIE
  • ZHANG JIAQING

Assignees

  • 安徽永正密封件有限公司

Dates

Publication Date
20260512
Application Date
20260321

Claims (10)

  1. 1. The photo-thermal response self-repairing rubber sealing ring is characterized by comprising the following raw materials in parts by weight: 100 parts of rubber base stock, 5-20 parts of double-wall microcapsules, 50-65 parts of reinforcing component, 5-10 parts of catalytic component, 2.5-3.5 parts of vulcanizing agent, 2-3 parts of cross-linking agent, 5-10 parts of plasticizer, 1-2 parts of antioxidant and 1-1.5 parts of anti-aging agent; the double-wall microcapsule comprises a capsule core, an inner-layer capsule wall and an outer-layer capsule wall from inside to outside, wherein the capsule core is dicyclopentadiene, the inner-layer capsule wall is urea formaldehyde resin, the outer-layer capsule wall is polyurea or polyurethane, and the outer-layer capsule wall carries photo-thermal conversion nano particles; the catalytic component is porous nano silicon dioxide loaded benzylidene bis (tricyclohexylphosphorus) ruthenium dichloride.
  2. 2. The photo-thermal response self-repairing rubber sealing ring according to claim 1, wherein the photo-thermal conversion nano particles are at least one of carbon nano tubes, graphene oxide and MXene materials.
  3. 3. The photo-thermal response self-repairing rubber sealing ring according to claim 1, wherein the preparation of the double-wall microcapsule is performed in two steps, and the specific steps are as follows: S1, uniformly mixing urea and formaldehyde solution, regulating the pH value to 7-8 by using triethanolamine aqueous solution, treating for 1h at 70 ℃ to obtain urea-formaldehyde resin prepolymer, adding dicyclopentadiene into ethylene-maleic anhydride copolymer aqueous solution, stirring for 1-1.5h at 300-500r/min to obtain DCPD emulsion, adding urea-formaldehyde resin prepolymer into DCPD emulsion, regulating the pH value of a system to 3.5-4 by using hydrochloric acid solution, heating to 55-65 ℃ for reaction for 3-5h, filtering after the reaction is finished, washing a filter cake by using absolute ethyl alcohol, and drying to obtain single-wall microcapsules; S2, dispersing the single-wall microcapsule in acetone, adding the photo-thermal conversion nano particle aqueous dispersion liquid, uniformly stirring, then dropwise adding diisocyanate, adding a chain extension component, stirring at room temperature for reaction for 3-5h, heating to 40-50 ℃, continuing to react for 1-2h, after the reaction is finished, carrying out suction filtration, washing a filter cake, and drying to obtain the double-wall microcapsule.
  4. 4. The photo-thermal response self-repairing rubber sealing ring according to claim 3, wherein the dosage ratio of urea, formaldehyde solution, dicyclopentadiene and ethylene-maleic anhydride copolymer aqueous solution in S1 is 7.4g:18-19mL:20-35g:150-250mL, the mass fraction of triethanolamine aqueous solution is 8-10%, the mass fraction of ethylene-maleic anhydride copolymer aqueous solution is 1-2%, and the mass fraction of hydrochloric acid solution is 1-3%.
  5. 5. The photo-thermal response self-repairing rubber sealing ring according to claim 3, wherein the dosage ratio of single-wall microcapsules, acetone, photo-thermal conversion nano particles, diisocyanate and chain extension components in S2 is 10g:100mL:0.5-1.5g:1-2g:0.43-0.86g.
  6. 6. A photo-thermal response self-repairing rubber sealing ring according to claim 3, wherein the chain extension component is an amine compound and/or an alcohol compound, the amine compound is at least one of ethylenediamine, diethylenetriamine and hexamethylenediamine, and the alcohol compound is at least one of ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol.
  7. 7. The photo-thermal response self-repairing rubber sealing ring according to claim 1, wherein the catalytic component comprises the following specific steps: Adding benzylidene bis (tricyclohexylphosphorus) ruthenium dichloride into dichloromethane, stirring uniformly, adding porous nano silicon dioxide, stirring and mixing for 4-6h under the protection of light and argon, and finally removing the dichloromethane by rotary evaporation to obtain the catalytic component.
  8. 8. The photo-thermal response self-repairing rubber sealing ring according to claim 7, wherein the mass ratio of the benzylidene bis (tricyclohexylphosphorus) ruthenium dichloride to the porous nano-silica is 1:3-5, the specific surface area of the porous nano-silica is not less than 250m 2 /g, and the average pore diameter of the porous nano-silica is 2-20nm.
  9. 9. The preparation method of the photo-thermal response self-repairing type rubber sealing ring is characterized by comprising the following steps of: Firstly, adding a rubber base material, a reinforcing component, a cross-linking agent, a plasticizer, an antioxidant and an anti-aging agent into an open mill, mixing for 8-12min at 60-75 ℃ to obtain a master batch, then adding a catalytic component into the master batch, mixing for 3-5min at 45 ℃ and a roll spacing of 0.5-1.0mm, and then adding double-wall microcapsules, mixing for 3-5min at a roll spacing of 1.5-2.0mm to obtain a mixed rubber; And secondly, adding a vulcanizing agent into the rubber compound, mixing for 3-5min at 35-45 ℃, and finally vulcanizing and forming to obtain the photo-thermal response self-repairing rubber sealing ring.
  10. 10. Use of the photo-thermal response self-repairing rubber seal ring according to any one of claims 1-8 in a dynamic or static sealing system.

Description

Photo-thermal response self-repairing rubber sealing ring and preparation method and application thereof Technical Field The invention belongs to the technical field of rubber products, and particularly relates to a photo-thermal response self-repairing type rubber sealing ring, and a preparation method and application thereof. Background Rubber seals are an essential elastic sealing element, and are an essential basic component in the modern industry. The device is mainly arranged at the connecting or moving gap of the parts such as the pipeline, the flange, the shaft lever and the like, and fills the gap by utilizing the high elastic deformation of the rubber material, thereby effectively blocking the leakage of the medium such as liquid, gas and the like. The functions of the hydraulic valve are not only limited by static sealing and leakage prevention, but also extend to the aspects of buffering and damping, compensating for thermal expansion and contraction, protecting interfaces and the like, and the hydraulic valve is widely applied to the key fields of building water supply and drainage, heating ventilation and air conditioning, automobile manufacturing, aerospace, petrochemical industry, hydraulic pneumatic systems and the like. Rubber failure, however, often results from initiation and propagation of microcracks. Once the traditional rubber material is damaged, the performance of the traditional rubber material is irreversibly reduced, and the traditional rubber material must be shut down and replaced, so that the maintenance cost is high and potential safety hazards exist. Inspired by the phenomenon of self-healing after biological injury, self-healing materials have become the leading research direction for prolonging the life of polymer materials. Among them, a self-healing system of the external aid type based on a microcapsule-embedded liquid-state healing agent has been intensively studied in thermosetting resins such as epoxy resins and has demonstrated potential. The basic principle is that microcapsules filled with repairing agent are pre-buried in the material, when the material generates cracks, the mechanical force of crack propagation can puncture the microcapsules, the repairing agent is released to the crack surface, and the repairing is realized through a preset catalyst or chemical reaction with a matrix. However, the direct grafting of this seemingly mature solution into rubber sealing material systems presents a great challenge: (1) The repairing agent has poor compatibility with rubber, and most repairing agents are difficult to be well compatible with rubber base materials, so that the mechanical properties of the base body are easy to be degraded; (2) The repair efficiency is low, the high elasticity of the rubber enables cracks to repeatedly open and close under stress, and the hydrophobic surface of the rubber is unfavorable for the flow, infiltration and bonding of the repair agent, so that the repair efficiency is low; (3) The triggering mode is not suitable for the traditional self-repairing dependent crack to automatically puncture the microcapsule, has low triggering efficiency for closing a tight fatigue crack, and the rubber is always in a dark and airtight space and lacks effective external triggering energy. Therefore, how to overcome the compatibility difficulty of the repairing agent and the high-crosslinking rubber base material and break through the limitation of a passive trigger mechanism on micro fatigue cracks, and develop a self-repairing rubber sealing ring with good performance is a problem to be solved at present. Disclosure of Invention The invention aims to provide a photo-thermal response self-repairing type rubber sealing ring, which solves the problem of poor compatibility of the existing repairing agent and a rubber base material, breaks through the limitation of a passive trigger mechanism on micro fatigue cracks, and finally obtains the sealing ring which can automatically repair internal damage caused by fatigue, abrasion or micro puncture under the irradiation of external near infrared light (NIR), thereby recovering the sealing performance and remarkably prolonging the service life. The second purpose of the invention is to provide a preparation method of the photo-thermal response self-repairing type rubber sealing ring. The invention further provides an application of the photo-thermal response self-repairing type rubber sealing ring. The aim of the invention can be achieved by the following technical scheme: The invention provides a photo-thermal response self-repairing rubber sealing ring, which comprises the following raw materials in parts by weight: 100 parts of rubber base stock, 5-20 parts of double-wall microcapsules, 50-65 parts of reinforcing component, 5-10 parts of catalytic component, 2.5-3.5 parts of vulcanizing agent, 2-3 parts of cross-linking agent, 5-10 parts of plasticizer, 1-2 parts of antioxidant and 1-1.5 parts of anti