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CN-121991510-A - Nanometer lanthanum oxide-carbon fiber-boron nitride synergistically modified silicone rubber and preparation method thereof

CN121991510ACN 121991510 ACN121991510 ACN 121991510ACN-121991510-A

Abstract

The invention provides nano lanthanum oxide-carbon fiber-boron nitride synergistic modified silicon rubber and a preparation method thereof, wherein the nano lanthanum oxide-carbon fiber-boron nitride synergistic modified silicon rubber comprises 8 components of 80-100 parts by mass of silicon rubber, 2-5 parts by mass of nano lanthanum oxide and the like, and further comprises 2-3 parts of specific compound antioxidant and 2-3 parts of processing aid, the preparation method comprises four steps of carbon fiber plasma pretreatment, and each technological parameter is defined. The comprehensive improvement of high temperature resistance, mechanical strength, fuel resistance and low temperature toughness of the silicone rubber composite material is realized, the process is controllable and suitable for industrial production, and the environmental protection performance is strong.

Inventors

  • LI XINGQIU
  • ZHANG HUALIN
  • ZHANG BAOHAI
  • ZHANG HUAFENG
  • GAO YONGZHI
  • GAO JINGXUAN

Assignees

  • 天津中冠汽车部件制造有限公司

Dates

Publication Date
20260508
Application Date
20260309

Claims (10)

  1. 1. The nanometer lanthanum oxide-carbon fiber-boron nitride synergistic modified silicon rubber composite material is characterized by comprising, by mass, 80-100 parts of silicon rubber, 2-5 parts of nanometer lanthanum oxide, 3-8 parts of carbon fiber, 4-10 parts of boron nitride, 3-8 parts of methyl silicone resin, 1.1-1.6 parts of vulcanizing agent, 1-3 parts of coupling agent and 5-12 parts of environment-friendly plasticizer.
  2. 2. The nano lanthanum oxide-carbon fiber-boron nitride synergistic modified silicone rubber composite material according to claim 1, wherein the particle size of the nano lanthanum oxide is 5-50 nm, the length of the carbon fiber is 50-200 μm, the diameter of the carbon fiber is 5-15 μm, the boron nitride is hexagonal boron nitride, and the particle size of the boron nitride is 10-100 nm.
  3. 3. The nano lanthanum oxide-carbon fiber-boron nitride synergistically modified silicone rubber composite material according to claim 1, wherein the silicone rubber is methyl vinyl silicone rubber, the vinyl content of the silicone rubber is 0.08% -0.16%, and the number average molecular weight of the silicone rubber is 58-62 ten thousand.
  4. 4. The nano lanthanum oxide-carbon fiber-boron nitride synergistic modified silicone rubber composite material according to claim 1 is characterized in that the coupling agent is one or two of a silane coupling agent and a titanate coupling agent, and the environment-friendly plasticizer is one or two of environment-friendly oil and environment-friendly silicone oil.
  5. 5. The nano lanthanum oxide-carbon fiber-boron nitride co-modified silicone rubber composite material according to claim 1, wherein the vulcanizing agent is one or more of 2, 4-dichloro benzoyl peroxide, di-tert-butyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and dicumyl peroxide.
  6. 6. The nano lanthanum oxide-carbon fiber-boron nitride synergistic modified silicone rubber composite material according to claim 1, wherein 2-3 parts of antioxidant is added into the modified silicone rubber composite material, the antioxidant is a compound mixture of antioxidant NBC and antioxidant 445 or antioxidant D, and the antioxidant NBC accounts for 75-95% of the total weight of the antioxidant.
  7. 7. The nano lanthanum oxide-carbon fiber-boron nitride synergistic modified silicone rubber composite material according to claim 1 or 6, wherein 2-3 parts of processing aid is added, and the processing aid is one or two of dispersing agent L-24 and waxy polyethylene.
  8. 8. A method for preparing the nano lanthanum oxide-carbon fiber-boron nitride synergistically modified silicone rubber composite material according to any one of claims 1-7, which is characterized by comprising the following steps: (1) Pretreating, namely treating the carbon fiber by plasma for 10-30 min, mixing the carbon fiber with nano lanthanum oxide, boron nitride and a coupling agent, and stirring the mixture at 300-500 rpm for 1-2 h at 80-100 ℃ to obtain modified filler; (2) Plasticating, namely adding the silicon rubber into an open mill, and plasticating until the Mooney viscosity ML (1+4) 100℃ is 40-60 to obtain base rubber; (3) Mixing, namely transferring the base rubber into an internal mixer, adding modified filler, methyl silicone resin, environment-friendly plasticizer and antioxidant and/or processing aid, mixing the antioxidant and the processing aid for 5-8 min at 120-130 ℃ and 50-120 rpm, adjusting the temperature to 100-105 ℃ for discharging, carrying out thin ventilation on the internal mixer for 3-4 times, hanging and airing the sheet, standing for 12 hours, adding vulcanizing agent, controlling the roller temperature of the internal mixer to be not more than 60 ℃, controlling the roller spacing to be 0.5-1.0 mm, carrying out thin ventilation for 4-5 times, and carrying out sheet discharging and cooling; (4) And (3) vulcanizing, namely placing the rubber compound obtained in the step (3) on an open mill for one time, and vulcanizing for 10-15 min at 160-180 ℃ and 10-15 MPa to obtain the nano lanthanum oxide-carbon fiber-boron nitride synergistic modified silicone rubber composite material.
  9. 9. The method according to claim 8, wherein the power of the plasma treatment in the step (1) is 100 to 300w and the vacuum degree is 0.05 to 0.09mpa.
  10. 10. Use of the nano lanthanum oxide-carbon fiber-boron nitride synergistically modified silicone rubber composite material according to any one of claims 1-7 in preparation of automobile fuel oil rubber tubes, automobile intercooler rubber tubes or automobile air conditioner pipeline rubber tubes.

Description

Nanometer lanthanum oxide-carbon fiber-boron nitride synergistically modified silicone rubber and preparation method thereof Technical Field The invention belongs to the technical field of rubber composite materials, and particularly relates to nanometer lanthanum oxide-carbon fiber-boron nitride synergistically modified silicone rubber and a preparation method thereof. Background With the development of the automobile industry to high performance and high reliability, the working environments of key parts such as automobile fuel oil rubber pipes, intercooler rubber pipes, air conditioner pipeline rubber pipes and the like are more severe. The pipeline is not only required to bear the corrosion of media such as fuel oil, refrigerant and the like for a long time, but also is required to adapt to the working conditions of wide temperature ranges from minus 40 ℃ to over 150 ℃, and simultaneously, extremely high requirements are provided for the mechanical strength, heat-resistant stability, ageing resistance and barrier property of the material. Silicone rubber has been a core substrate for preparing such automotive hoses because of its excellent high and low temperature resistance, weather resistance and chemical stability, wherein methyl vinyl silicone rubber is widely used in related fields by virtue of moderate crosslinking activity and mechanical basis. However, pure silicone rubber has inherent defects of low mechanical strength, insufficient heat conductivity, easy aging and degradation at high temperature for a long time and the like, and is difficult to completely meet the use requirements of key pipelines of modern automobiles. In the prior art, researchers mostly adopt single filler or binary composite filler to modify silicon rubber, such as adding carbon fiber to improve mechanical strength, introducing boron nitride to improve heat conducting property, adding metal oxide to enhance ageing resistance and the like. However, a single modification system often has a short performance board, and the modification effect is not expected due to the problems of uneven dispersion of filler, poor interface compatibility and the like, so that the synergistic improvement of mechanical properties, heat resistance, ageing resistance and other multiple performances is difficult to realize. In addition, the filler pretreatment process adopted by the partial modification scheme is simple, so that the filler agglomeration phenomenon is further aggravated, and the comprehensive performance stability of the composite material is affected. Meanwhile, the silicon rubber material for the existing automobile rubber tube still has room for improvement in the aspects of environmental protection and long-term service reliability. The plasticizer, the processing aid and other parts used in the traditional modification process have environmental protection hidden trouble, and after the material contacts fuel oil for a long time and is subjected to wide temperature range circulation, the problems of mechanical property attenuation, aging cracking and the like are easy to occur, so that the service life of a pipeline and the driving safety are seriously influenced. Therefore, developing a silicone rubber composite material which realizes the cooperative improvement of mechanical strength, heat-resistant stability, ageing resistance and environmental protection through the cooperative modification of the multi-element filler, optimization of the filler pretreatment process and environmental protection component selection becomes an urgent need for solving the performance bottleneck of the key pipeline material of the current automobile. Disclosure of Invention In order to solve the technical problems, the invention provides the nano lanthanum oxide-carbon fiber-boron nitride synergistic modified silicone rubber and the preparation method thereof, and the comprehensive improvement of high temperature resistance, mechanical strength, fuel resistance and low temperature toughness of the silicone rubber composite material is realized through the ternary synergistic modification and optimized preparation process of nano lanthanum oxide, carbon fiber and boron nitride, and the process is controllable, suitable for industrial production, strong in environmental protection and capable of accurately matching the working condition requirements of key rubber tubes of automobiles. The technical scheme adopted by the invention is as follows: The nanometer lanthanum oxide-carbon fiber-boron nitride synergistic modified silicon rubber composite material comprises, by mass, 80-100 parts of silicon rubber, 2-5 parts of nanometer lanthanum oxide, 3-8 parts of carbon fiber, 4-10 parts of boron nitride, 3-8 parts of methyl silicone resin, 1.1-1.6 parts of vulcanizing agent, 1-3 parts of coupling agent and 5-12 parts of environment-friendly plasticizer. Further, the particle size of the nano lanthanum oxide is 5-50 nm, the length of the carbon fiber