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CN-122011601-A - Low-odor modified ethylene propylene diene monomer composite material

CN122011601ACN 122011601 ACN122011601 ACN 122011601ACN-122011601-A

Abstract

The invention provides a low-odor modified ethylene propylene diene monomer composite material, which adopts a hydrothermal method to prepare carbon tube-molecular sieve composite fillers with different acidized single-wall carbon nano tube contents and uses the carbon tube-molecular sieve composite fillers for reinforcing ethylene propylene diene monomer. By optimizing the content of the single-walled carbon nanotubes in the molecular sieve, the mechanical property, the odor grade and the thermal property of the material can be obviously improved.

Inventors

  • WU YADONG
  • JIN HUILE
  • LI JUN
  • Peng Xuqiang
  • WANG SHUN

Assignees

  • 温州大学新材料与产业技术研究院
  • 温州大学

Dates

Publication Date
20260512
Application Date
20260207

Claims (10)

  1. 1. The low-odor modified ethylene propylene diene monomer composite material is characterized in that the low-odor modified ethylene propylene diene monomer composite material is obtained by compounding carbon tube-molecular sieve composite filler serving as filler in ethylene propylene diene monomer, wherein the carbon tube-molecular sieve composite filler is obtained by compounding molecular sieve seed crystals and acidified single-wall carbon nanotubes.
  2. 2. The low-odor modified ethylene propylene diene monomer composite material according to claim 1, wherein the composite mass ratio of the carbon tube-molecular sieve composite filler to the ethylene propylene diene monomer is 1 (8-12).
  3. 3. The low-odor modified ethylene propylene diene monomer composite material of claim 1, wherein the mass ratio of the molecular sieve seed crystal to the acidified single-walled carbon nanotubes is 1 (0.3-1.5).
  4. 4. The low odor modified ethylene propylene diene monomer rubber composite material of claim 1, wherein the preparation method of the carbon tube-molecular sieve composite filler comprises the following steps: s1, synthesizing molecular sieve seed crystals, namely dissolving sodium metaaluminate and sodium hydroxide in pure water to form a solution A, adding tetrapropylammonium hydroxide and pure water into silica sol, stirring uniformly to form a solution B, dripping the solution A into the solution B, stirring uniformly to form a solution C, performing hydrothermal reaction on the solution C at 160-200 ℃ for 60-80 hours, washing and drying a product, and calcining the product at 500-600 ℃ for 3-5 hours to obtain the molecular sieve seed crystals; S2, preparing an acidified single-walled carbon nano dispersion, namely adding the single-walled carbon nano tubes into a concentrated acid solution, stirring to obtain mixed acid containing the single-walled carbon nano tubes, adding the mixed acid into deionized water, standing and layering to form supernatant and lower turbid liquid, continuously adding the lower turbid liquid into the deionized water, standing and layering until the pH value of the lower turbid liquid is greater than 3, filtering and washing to obtain the acidified single-walled carbon nano tubes, and dispersing the acidified single-walled carbon nano tubes into the deionized water to obtain the acidified single-walled carbon nano dispersion; s3, adding molecular sieve seed crystals and deionized water into silica sol, stirring uniformly, adding the solution A into the silica sol to obtain a solution D, adding the acidified single-wall carbon nanotube dispersion liquid, stirring uniformly to form a solution E, pouring the mixed solution E into a reaction kettle, reacting in an oven at 160-200 ℃ for 60-80 hours, filtering, washing and drying the reaction product to obtain the carbon tube-molecular sieve composite filler.
  5. 5. The low odor modified ethylene propylene diene monomer rubber composite material as set forth in claim 4, wherein in step S1, the mass ratio of sodium metaaluminate, sodium hydroxide, tetrapropylammonium hydroxide and silica in silica sol is 1 (4.5-6.5): 28-32): 70-75.
  6. 6. The low odor modified ethylene propylene diene monomer rubber composite material as claimed in claim 4, wherein in the step S2, the concentrated acid solution is obtained by mixing concentrated sulfuric acid and concentrated nitric acid according to a volume ratio (2-4): 1 and stirring at 60-80 ℃ for 6-8 h.
  7. 7. The low odor modified ethylene propylene diene monomer composite material of claim 4, wherein in step S3, the reaction product is filtered and washed to be neutral, and baked for 3-5 hours at 100-140 ℃ to obtain the carbon tube-molecular sieve composite filler.
  8. 8. The low odor modified ethylene propylene diene monomer composite material according to any one of claims 1 to 7, characterized in that it comprises the following steps: (A) Fully mixing ethylene propylene diene monomer rubber and carbon tube-molecular sieve composite filler at 40-60 ℃, sequentially adding zinc oxide, stearic acid, vulcanizing agent and auxiliary vulcanizing agent, and uniformly mixing to obtain a mixed sizing material; (B) And vulcanizing and curing the mixed rubber material at 150-190 ℃ and 5-15MPa for 5-15min to obtain the modified ethylene propylene diene monomer.
  9. 9. The low-odor modified ethylene propylene diene monomer composite material according to claim 8, wherein the parts ratio of ethylene propylene diene monomer to carbon tube-molecular sieve composite filler to zinc oxide to vulcanizing agent to auxiliary vulcanizing agent is 100 (5-25) (0.5-2) (1-3).
  10. 10. The low odor modified ethylene propylene diene monomer composite material of claim 8, wherein the vulcanizing agent is bifive and the auxiliary vulcanizing agent is TAIC.

Description

Low-odor modified ethylene propylene diene monomer composite material Technical Field The invention relates to the technical field of ethylene propylene diene monomer rubber, in particular to a low-odor modified ethylene propylene diene monomer rubber composite material. Background Ethylene Propylene Diene Monomer (EPDM) has been widely used in various fields such as automobiles, buildings, electronic and power cables, etc., because of its excellent weather resistance, aging resistance, chemical corrosion resistance and electrical insulation properties. For example, EPDM is widely used in the automotive field to manufacture seals, hydraulic brake seals, ventilation ducts, and the like. However, EPDM also has some short performance panels, such as used as automotive weatherstrips, which tend to release unpleasant odors when exposed to sun or at higher ambient temperatures, with higher odor levels, severely impacting the riding experience of the passengers. In 2011 of China, the national publication of guidelines for evaluating the air quality in passenger cars prescribes the concentration requirements of 8 volatile organic compounds in the passenger cars. As can be seen, the national requirements for air quality in vehicles are increasing, which forces EPDM to develop in a low odor, environmentally friendly direction on automotive upholstery. The high odor rating of EPDM is believed to be related to the incomplete polymerization of residual odorous ethylene, propylene monomers or odorous vulcanization aids used during rubber processing. To overcome this difficulty, researchers have generally adopted a high odor vulcanization aid replacement strategy, i.e., a low or odorless vulcanization aid is used in place of the high odor aid, thereby achieving vulcanization and odor reduction of the rubber. For example, the Qingdao university Duchang uses several environment-friendly accelerators and deodorant to prepare environment-friendly EPDM, and the environment-friendly accelerator which is better than the common accelerator can be found to have a certain deodorizing effect, but can influence the positive vulcanization time. The Tianjin neutralization gum company Chen Qiaona prepares low odor EPDM by using low odor environment-friendly raw materials and accelerators with relatively large molecular mass. The university of northeast Cui Shuangqing uses bio-based TPO in combination with bio-based EPDM to prepare an environmentally friendly EPDM. The new energy development institute Zheng Hong and the like of the first automobile group company in China mention that when researching the application progress of the EPDM on automobiles, the whole automobile factory uses an EPDM rubber material formula without a nitrosamine vulcanization accelerating system, and environmental protection additives and accelerators are comprehensively adopted, so that the odor grade can be within 3.5 minutes (80 ℃ and 2 hours). However, the above studies have been conducted from low odor adjuvants and raw materials, and limited the range of choices for adjuvants and raw materials. At present, research on improving the odor performance of EPDM by synthesizing a molecular sieve with high porosity and high specific surface area through a physical adsorption principle has not been reported yet. Disclosure of Invention The invention aims to overcome the defects and the shortcomings of the prior art and provide a low-odor modified ethylene propylene diene monomer composite material. The technical scheme adopted by the invention is that the low-odor modified ethylene propylene diene monomer composite material is obtained by compounding carbon tube-molecular sieve composite filler serving as filler in ethylene propylene diene monomer, wherein the carbon tube-molecular sieve composite filler is obtained by compounding molecular sieve seed crystals and acidified single-wall carbon nanotubes. Preferably, the composite mass part ratio of the carbon tube-molecular sieve composite filler to the ethylene propylene diene monomer rubber is 1 (8-12). Preferably, the mass ratio of the molecular sieve seed crystal to the acidified single-walled carbon nanotube is 1 (0.3-1.5). Preferably, the preparation method of the carbon tube-molecular sieve composite filler comprises the following steps: s1, synthesizing molecular sieve seed crystals, namely dissolving sodium metaaluminate and sodium hydroxide in pure water to form a solution A, adding tetrapropylammonium hydroxide and pure water into silica sol, stirring uniformly to form a solution B, dripping the solution A into the solution B, stirring uniformly to form a solution C, performing hydrothermal reaction on the solution C at 160-200 ℃ for 60-80 hours, washing and drying a product, and calcining the product at 500-600 ℃ for 3-5 hours to obtain the molecular sieve seed crystals; S2, preparing an acidified single-walled carbon nano dispersion, namely adding the single-walled carbon nano tubes into a concentrate