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CN-122011511-A - Nanometer clay composite reinforcing agent for rubber and preparation method thereof

CN122011511ACN 122011511 ACN122011511 ACN 122011511ACN-122011511-A

Abstract

The invention discloses a nanoclay composite reinforcing agent for rubber, which comprises 50-60 parts of carbon black and 5-10 parts of modified nanoclay, wherein the modified nanoclay is the nanoclay which is synergistically modified by a multifunctional group organic modifier and a functional ionic liquid. The composite reinforcing agent not only realizes the high dispersibility and strong interface combination of the nano clay in the rubber matrix, effectively reduces the carbon black consumption and improves the reinforcing efficiency, but also endows the material with self-repairing and reworkable characteristics by introducing dynamic reversible covalent bonds, and simultaneously has low heat generation, high wear resistance and long durability. The invention also discloses a preparation method of the nano clay composite reinforcing agent for rubber.

Inventors

  • WANG SHAOXIONG

Assignees

  • 宁波嘉和新材料科技有限公司

Dates

Publication Date
20260512
Application Date
20260317

Claims (10)

  1. 1. A nanoclay composite reinforcement for rubber, the composite reinforcement comprising: 40-50 parts of carbon black and 5-10 Parts of modified nanoclay; Wherein the modified nanoclay is the nanoclay which is synergistically modified by a multifunctional group organic modifier and a functional ionic liquid.
  2. 2. The nanoclay composite reinforcing agent for rubber as claimed in claim 1, wherein the multi-functional organic modifier is a four-arm star-shaped molecule having a triethoxysilane group at the end of each arm.
  3. 3. The nanoclay composite reinforcement for rubber as recited in claim 1, wherein each arm of the multifunctional organic modifier has a DA bond.
  4. 4. The nanoclay composite reinforcing agent for rubber as claimed in claim 1, wherein the center of the multifunctional organic modifier has disulfide bonds.
  5. 5. The nanoclay composite reinforcing agent for rubber according to claim 1, wherein the functional ionic liquid is at least one of 1-vinyl-3-ethylimidazole bromide, 1-vinyl-3-butylimidazole bromide, and 1-allyl-3-butylimidazole bromide.
  6. 6. The preparation method of the nanoclay composite reinforcing agent for rubber is characterized by comprising the following steps of: S1, adding triethoxy-2-furan silane and N-allyl maleimide into a reaction vessel containing an organic solvent to perform Diels-Alder cycloaddition reaction to obtain a furan-maleimide DA addition intermediate product containing allyl and triethoxysilane groups; S2, adding the furan-maleimide DA addition intermediate product obtained in the step S1 and dithiodiamine into an organic solvent according to a molar ratio of 4-6:1, adding a transition metal catalyst and n-butyllithium, and stirring and reacting for 8-16 hours at 80-120 ℃ to form a four-arm star-shaped molecular multifunctional organic modifier; S3, ultrasonically dispersing the nano clay in a solvent to prepare clay dispersion liquid with the mass concentration of 5-15%, adding functional ionic liquid, stirring and reacting for 2-6 hours at 50-80 ℃ to enable the ionic liquid to intercalate between the nano clay layers, and obtaining ionic liquid intercalation modified clay dispersion liquid; S4, adding the star-shaped multifunctional group organic modifier obtained in the step S2 into the ionic liquid intercalation modified clay dispersion liquid obtained in the step S3, continuously stirring at 60-90 ℃ for reaction for 4-8 hours, and centrifuging, washing and drying after the reaction is finished to obtain modified nano clay; and S5, adding 5-10 parts of the modified nanoclay obtained in the step S4 and 40-50 parts of carbon black into a high-speed mixer in proportion, and mixing for 10-30 min at 80-120 ℃ to obtain the nanoclay composite reinforcing agent for rubber.
  7. 7. The method for preparing a nanoclay composite reinforcing agent for rubber as set forth in claim 6, wherein in step S1, the Diels-Alder cycloaddition reaction is performed in an inert atmosphere, the reaction temperature is controlled to be 50-80 ℃, and the reaction time is 6-12 hours.
  8. 8. The method for producing a nanoclay composite reinforcing agent for rubber as set forth in claim 6, wherein said dithiodiamine is at least one of 3,3' -dithiobis-propionamide, 2' -dithiobis (ethylamine), 4' -dithiodiphenylamine.
  9. 9. The method for preparing a nanoclay composite reinforcing agent for rubber as set forth in claim 6, wherein said transition metal catalyst is at least one of palladium chloride, bis (triphenylphosphine) palladium dichloride, and palladium acetate.
  10. 10. The method for preparing the nano-clay composite reinforcing agent for rubber according to claim 6, wherein the addition amount of the functional ionic liquid is 2-10% of the mass of the nano-clay, and the addition amount of the multifunctional organic modifier is 5-15% of the mass of the nano-clay.

Description

Nanometer clay composite reinforcing agent for rubber and preparation method thereof Technical Field The invention relates to the technical field of rubber reinforcing agents, in particular to a nano clay composite reinforcing agent for rubber and a preparation method thereof. Background Rubber materials are widely used in the fields of tires, conveyor belts, sealing elements, shock absorbing components and the like due to excellent high elasticity, wear resistance and damping characteristics. In order to improve the mechanical properties and the service life of rubber, a reinforcing agent is usually required to be added, wherein carbon black is the most traditional and widely applied reinforcing material, and can remarkably improve the tensile strength, the tearing strength and the wear resistance of the rubber. However, the traditional carbon black reinforcing system has obvious defects that the high filling amount leads to high heat generation of the sizing material and deterioration of dynamic performance, and mainly depends on petroleum resources, so that the traditional carbon black reinforcing system does not meet the requirement of green sustainable development. In recent years, nanoclay, which is a layered silicate material, has been considered as an ideal candidate for replacing or partially replacing carbon black due to its wide source, low cost, high aspect ratio and barrier effect. The lamellar structure of the nano clay can form a labyrinth effect in rubber, so that gas and liquid permeation can be effectively blocked, and the air tightness and solvent resistance are improved. However, nanoclay has two major bottlenecks in practical application, namely strong interlayer electrostatic attraction, extremely easy agglomeration, difficulty in realizing nanoscale dispersion in a rubber matrix, and poor compatibility with rubber due to hydrophilic and oleophobic surfaces and weak interface bonding, so that the stress transfer efficiency is low, and the reinforcing effect is far from theoretical expectation. Organic modification is a key means to improve the dispersibility and interfacial compatibility of nanoclays. Although the traditional alkyl ammonium salt intercalation agent can enlarge interlayer spacing, the thermal stability is insufficient, and the intercalation agent is easy to decompose at the rubber processing temperature, so that interlayer collapse and interface defects are caused. The silane coupling agent is another type of common modifier, but the traditional monofunctional or difunctional silane has few action points with clay, low grafting density, difficult formation of strong interface bonding, and lack of dynamic response characteristics, and cannot meet the comprehensive requirements of modern rubber products on long durability and functionality. Therefore, development of a novel efficient modification technology, realization of high dispersion and strong interfacial bonding of the nanoclay in rubber and synergistic effect with carbon black, and still remain technical problems to be solved in the rubber industry. Disclosure of Invention In view of the shortcomings of the prior art, the invention provides a nano clay composite reinforcing agent for rubber, which aims to solve the technical problems that the traditional carbon black reinforced rubber is high in heat generation, poor in nano clay dispersibility and weak in interface bonding, and the traditional organic modifier is insufficient in thermal stability, and is difficult to combine high reinforcement and dynamic performance. In order to achieve the above purpose, the invention adopts the following technical scheme: a nanoclay composite reinforcement for rubber, the composite reinforcement comprising: 40-50 parts of carbon black and 5-10 Parts of modified nanoclay; Wherein the modified nanoclay is the nanoclay which is synergistically modified by a multifunctional group organic modifier and a functional ionic liquid. As a preferable technical scheme, the multifunctional organic modifier is a four-arm star-shaped molecule containing triethoxysilane groups at the tail end of each arm. As a preferred embodiment, each arm of the multifunctional organic modifier has a DA bond. As a preferable technical scheme, the center of the multifunctional organic modifier is provided with disulfide bond. As a preferable technical scheme, the functional ionic liquid is at least one of 1-vinyl-3-ethyl imidazole bromide, 1-vinyl-3-butyl imidazole bromide and 1-allyl-3-butyl imidazole bromide. In another aspect, the present invention provides a method for preparing a nanoclay composite reinforcing agent for rubber, the method comprising the steps of: The preparation method comprises the steps of S1, adding triethoxy-2-furansilane and N-allyl maleimide into a reaction container containing an organic solvent for Diels-Alder cycloaddition reaction to obtain a furan-maleimide DA addition intermediate product containing allyl groups and triethoxy