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CN-122011536-A - Nano-reinforced silane crosslinked chloroprene rubber composition and preparation method and application thereof

CN122011536ACN 122011536 ACN122011536 ACN 122011536ACN-122011536-A

Abstract

The invention discloses a nano-reinforced silane crosslinked chloroprene rubber composition, and a preparation method and application thereof, and belongs to the technical field of high-performance rubber materials. The technical scheme is that the nano-reinforced chloroprene rubber comprises, by weight, 100 parts of chloroprene rubber, 5-30 parts of a nano-reinforced phase, 2-10 parts of a silane cross-linking agent, 0.5-5 parts of an ionic liquid modifier, 3-15 parts of a bio-based plasticizer, 0.5-3 parts of a moisture absorber, 0.1-1.5 parts of an organotin catalyst, 1-4 parts of an anti-aging agent and 1-5 parts of a processing aid. The vulcanized rubber prepared by the method has excellent heat aging resistance, ultralow compression set, enhanced mechanical properties and excellent barrier properties, simultaneously completely avoids the problem of heavy metal environmental protection of the traditional metal oxide vulcanization system, and can be widely applied to high-end fields such as aerospace sealing parts, deep sea cable jackets, new energy automobile rubber tubes and the like.

Inventors

  • BAI YANG
  • SUN LIANFA
  • LI JUN
  • HU JIAXIN
  • Shao Zhaorui
  • WANG DEGONG
  • MA LONGFEI
  • ZHANG SHUJUN
  • ZHANG BAOLONG
  • SONG LIANGHE
  • WANG HUAIAN
  • DOU LIMEI
  • WANG ZEPENG
  • WU JIAN
  • TIAN ZHIMING

Assignees

  • 唐山华通特种线缆制造有限公司
  • 河北华通线缆集团股份有限公司

Dates

Publication Date
20260512
Application Date
20260318

Claims (10)

  1. 1. The nanometer reinforced silane crosslinked chloroprene rubber composition is characterized by comprising, by weight, 100 parts of chloroprene rubber, 5-30 parts of a nanometer reinforcing phase, 2-10 parts of a silane crosslinking agent, 0.5-5 parts of an ionic liquid modifier, 3-15 parts of a bio-based plasticizer, 0.5-3 parts of a moisture absorber, 0.1-1.5 parts of an organotin catalyst, 1-4 parts of an anti-aging agent and 1-5 parts of a processing aid.
  2. 2. A nano-reinforced silane crosslinked neoprene composition according to claim 1, wherein the nano-reinforced phase is surface functionalized nano-silica and/or carboxylated carbon nanotubes, the surface functionalization being in situ modification by silane coupling agent KH-550 or KH-590.
  3. 3. The multidimensional reinforced silane crosslinked chlorosulfonated polyethylene nanocomposite material according to claim 2, wherein the particle size of the nano silicon dioxide is 10-50nm, the specific surface area is more than or equal to 200m2/g, the diameter of the carboxylated carbon nanotube is 10-30nm, the length is 1-10 mu m, and the carboxyl content is 2-5wt%.
  4. 4. A nano-reinforced silane crosslinked chloroprene rubber composition according to claim 1 or 3, wherein said silane crosslinking agent is one or a mixture of two or more of gamma-aminopropyl triethoxysilane, gamma-mercaptopropyl trimethoxysilane and bis- (gamma-triethoxysilylpropyl) tetrasulfide.
  5. 5. A nano-reinforced silane crosslinked chloroprene rubber composition according to claim 1 or 3, wherein said ionic liquid modifier is one or more of 1-butyl-3-methylimidazole hexafluorophosphate, 1-allyl-3-methylimidazole chloride or 1-ethyl-3-methylimidazole dicyan amine salt.
  6. 6. The nano-reinforced silane crosslinked chloroprene rubber composition of claim 1 or 3, wherein said bio-based plasticizer is one or more of epoxidized soybean oil, castor oil based polyol ester or cardanol based plasticizer.
  7. 7. The nano-reinforced silane crosslinked chloroprene rubber composition according to claim 1 or 3, wherein the moisture absorbent is calcium oxide, magnesium oxide or molecular sieve powder, the organotin catalyst is dibutyltin dilaurate or dibutyltin diacetate, and the antioxidant is one or more of antioxidant RD, antioxidant 4010NA or antioxidant MMBI.
  8. 8. A method of preparing a nano-reinforced silane crosslinked neoprene composition according to any one of claims 1-7, comprising the steps of: (1) Nano reinforcing phase pretreatment, namely dispersing nano silicon dioxide and/or carboxylated carbon nano tubes in ethanol solution, adding a silane coupling agent KH-550 or KH-590, stirring and reacting for 2-4 hours at 60-80 ℃, filtering and drying to obtain a surface functionalized nano reinforcing phase; (2) Adding neoprene raw rubber into an internal mixer, plasticating to a wrapping roller, sequentially adding a surface functionalized nano reinforcing phase, an ionic liquid modifier, a bio-based plasticizer, a hygroscopic agent, an anti-aging agent and a processing aid, mixing for 10-15 minutes at 80-100 ℃, discharging rubber to obtain master batch, and standing for 8-12 hours; (3) Final milling, namely, putting the master batch on an open mill again, adding a silane cross-linking agent and an organotin catalyst at 40-50 ℃, carrying out thin pass for 5-8 times, and discharging after uniform milling; (4) Vulcanizing and molding, namely placing the final rubber into a mold, and vulcanizing in a first stage on a flat vulcanizing machine at 160-180 ℃ under 10-15MPa for positive vulcanization time t90; (5) And (3) post-crosslinking treatment, namely placing the product obtained after the first-stage vulcanization in a constant temperature and humidity box, wherein the temperature is 70-95 ℃, the relative humidity is 70-95%, and the time is 12-36 hours, so that the full hydrolytic condensation of silane and the in-situ bonding of a nano reinforcing phase are completed.
  9. 9. The method of claim 8, wherein the post-crosslinking step (5) is performed using a gradient heating process, which comprises treating at 70℃for 6 hours, heating to 85℃for 12 hours, and treating at 95℃for 6 hours.
  10. 10. Use of the nano-reinforced silane crosslinked neoprene composition according to any one of claims 1-7 for the preparation of aerospace seals, deep sea cable jackets, new energy automobile high pressure hoses or radiation resistant sealing articles for nuclear power plants.

Description

Nano-reinforced silane crosslinked chloroprene rubber composition and preparation method and application thereof Technical Field The invention relates to a nano-reinforced silane crosslinked chloroprene rubber composition, and a preparation method and application thereof, and belongs to the technical field of high-performance rubber materials. Background Neoprene (CR) is one of the earliest synthetic rubbers to realize industrialization, and is widely applied in the fields of wires and cables, automobile industry, aerospace and the like due to the excellent oil resistance, weather resistance, flame retardance and mechanical property. However, with the continuous improvement of the requirements of modern industry on material performance, especially in extreme environments such as deep sea exploration, new energy automobiles, nuclear energy utilization and the like, the heat resistance, compression set resistance and long-term service life of the traditional neoprene are difficult to meet the requirements. Traditional neoprene vulcanization systems use metal oxides (zinc oxide/magnesium oxide) in combination with sulfur or sulfur donors. The system has the inherent defects of (1) environmental protection problems that zinc ions are released to pollute the environment in the vulcanization process, the content of heavy metals in finished products is limited, and the requirements of international environmental protection regulations such as RoHS, REACH and the like are difficult to meet, (2) reversion that a cross-linked network mainly comprising polysulfide bonds is easy to break under the condition of high temperature or long-time oversulfur, so that the performance is rapidly reduced, and (3) compression set is large, and the cross-linked network formed by the traditional vulcanization system is uneven, stress relaxation is serious, so that the long-term reliability of a sealing element is affected. The silane crosslinking technology is successfully applied to polyethylene (silane crosslinked polyethylene cable material) and partially saturated rubber, the principle is that alkoxy groups of silane are hydrolyzed in moisture to generate silanol, silanol is condensed to form a stable-Si-O-Si-ether bond network, and the crosslinking bond energy (to 422 kJ/mol) is far higher than C-Sx-C bond (to 250 kJ/mol), so that the silane crosslinked polyethylene cable material has excellent heat resistance and ageing resistance. However, the direct application of silane crosslinking technology to neoprene presents multiple challenges including (1) high polarity of CR molecular chains, poor compatibility with common silanes, (2) interference of CR common acidic fillers (e.g., white carbon black) with silane hydrolysis-condensation reaction equilibrium, and (3) difficulty in forming uniform, high density crosslinked networks in CR with conventional silane crosslinking systems. In recent years, research is being attempted to improve the dispersibility of carbon nanotubes in chloroprene rubber by using ionic liquid, so that the mechanical and dielectric properties of the composite material are improved to a certain extent. However, the technology is still limited to the traditional metal oxide/sulfur vulcanization system, the cross-linked network nature is unchanged, and the problems of low cross-linked bond energy, poor heat aging resistance, large compression set, heavy metal environmental protection and the like still exist. Therefore, how to radically innovate the crosslinked network while improving filler dispersion is a key problem to be solved in the art. Disclosure of Invention The invention aims to provide a nano-reinforced silane crosslinked chloroprene rubber composition, a preparation method and application thereof, and the comprehensive improvement of the comprehensive performance of the chloroprene rubber is realized by constructing a nano-reinforced-chemical crosslinked dual-network structure, so that the requirements of the high-end application field on the material strictly can be met, and the problems in the background technology are solved. The technical scheme of the invention is as follows: The nanometer reinforced silane crosslinked chloroprene rubber composition comprises, by weight, 100 parts of chloroprene rubber, 5-30 parts of a nanometer reinforcing phase, 2-10 parts of a silane crosslinking agent, 0.5-5 parts of an ionic liquid modifier, 3-15 parts of a bio-based plasticizer, 0.5-3 parts of a moisture absorber, 0.1-1.5 parts of an organotin catalyst, 1-4 parts of an anti-aging agent and 1-5 parts of a processing aid. Further, the nano reinforcing phase is nano silicon dioxide with surface functionalization and/or carboxylated carbon nano tubes, and the surface functionalization is in-situ modification by a silane coupling agent KH-550 or KH-590. Further, the particle size of the nano silicon dioxide is 10-50nm, the specific surface area is more than or equal to 200m < 2 >/g, the diameter of the carbo