Search

CN-122011613-A - Multidimensional reinforced silane crosslinked chlorosulfonated polyethylene nanocomposite and preparation method and application thereof

CN122011613ACN 122011613 ACN122011613 ACN 122011613ACN-122011613-A

Abstract

The invention relates to a multidimensional reinforced silane crosslinked chlorosulfonated polyethylene nanocomposite and a preparation method and application thereof, belonging to the technical field of high-performance special rubber composite materials. The technical scheme is that the composite material comprises, by weight, 100 parts of chlorosulfonated polyethylene, 3-15 parts of a compound silane crosslinking system, 5-30 parts of a multidimensional nano reinforcing phase, 1-8 parts of a hyperbranched polymer modifier, 5-20 parts of an environment-friendly plasticizer, 0.1-2 parts of a catalyst, 10-60 parts of a filler and 2-8 parts of a functional auxiliary agent. The material is obviously superior to the prior art in heat resistance grade, mechanical property, chemical medium resistance, electrical insulation property, compression set and the like, and can be widely applied to the fields of high-end equipment for extreme environments such as nuclear power cables, deep sea petroleum exploitation, new energy automobiles, aerospace, geothermal exploration 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 composite material is characterized by comprising, by weight, 100 parts of chlorosulfonated polyethylene, 3-15 parts of a compound silane crosslinking system, 5-30 parts of a multidimensional nanometer reinforcing phase, 1-8 parts of a hyperbranched polymer modifier, 5-20 parts of an environment-friendly plasticizer, 0.1-2 parts of a catalyst, 10-60 parts of a filler and 2-8 parts of a functional auxiliary agent.
  2. 2. The multi-dimensional reinforced silane crosslinked chlorosulfonated polyethylene nanocomposite is characterized in that the compound silane crosslinking system is formed by compounding grafted silane and crosslinked silane according to the mass ratio of 1:0.3-1:2, wherein the grafted silane is at least one of vinyl trimethoxy silane, vinyl triethoxy silane or gamma-methacryloxypropyl trimethoxy silane, and the crosslinked silane is at least one of gamma-aminopropyl triethoxy silane, gamma-glycidoxypropyl trimethoxy silane or bis- [ gamma- (triethoxy silicon) propyl ] tetrasulfide.
  3. 3. The multi-dimensional reinforced silane crosslinked chlorosulfonated polyethylene nanocomposite material of claim 1, wherein the multi-dimensional nano reinforcement phase is a multi-component compounding system of functionalized zero-dimensional nano particles, one-dimensional nano materials and two-dimensional nano materials; the zero-dimensional nano particles are nano silicon dioxide with amino groups or epoxy groups grafted on the surfaces, the particle size is 5-30nm, the one-dimensional nano material is carboxylated or hydroxylated carbon nano tube, the diameter is 10-30nm, the length is 1-20 mu m, the two-dimensional nano material is layered double hydroxide or modified montmorillonite, the thickness of a sheet layer is 1-3nm, the diameter-thickness ratio is more than 100, and the mass ratio of the three is zero-dimensional, one-dimensional, two-dimensional=1:0.1-0.5:0.2-1.
  4. 4. A multi-dimensional reinforced silane crosslinked chlorosulfonated polyethylene nanocomposite according to claim 1 or 3, wherein the hyperbranched polymer modifier is at least one of amino-terminated hyperbranched polyester, hydroxyl-terminated hyperbranched polyamide or hyperbranched polysiloxane, the number average molecular weight of which is 2000-20000, and the branching degree is not less than 0.6.
  5. 5. The multi-dimensional reinforced silane crosslinked chlorosulfonated polyethylene nanocomposite according to claim 1 or 3, wherein the environment-friendly plasticizer is at least one of a polyester plasticizer, an epoxy fatty acid methyl ester plasticizer or a citrate plasticizer, and the catalyst is at least one of dibutyl tin dilaurate, dibutyl tin diacetate or an organobismuth catalyst.
  6. 6. A multi-dimensional reinforced silane crosslinked chlorosulfonated polyethylene nanocomposite according to claim 1 or 3, wherein the filler is at least one of calcined clay, talcum powder and mica powder, and the functional auxiliary agent comprises an antioxidant, a light stabilizer, an anti-aging agent and a processing auxiliary agent.
  7. 7. A method of preparing the multi-dimensionally reinforced silane crosslinked chlorosulfonated polyethylene nanocomposite of any one of claims 1-6, comprising the steps of: (1) Dispersing nano silicon dioxide, carbon nano tube and layered double hydroxide in ethanol/water mixed solvent according to proportion, adding silane coupling agent KH-560, regulating pH to 4-5, ultrasound-assisted reacting for 2-4 hours at 60-80 ℃, filtering, washing, vacuum drying to obtain synergetic multi-dimensional nano reinforcing phase; (2) Pre-dispersing the hyperbranched polymer, namely pre-mixing chlorosulfonated polyethylene and a hyperbranched polymer modifier in an internal mixer for 5-10 minutes at the temperature of 90-110 ℃ to uniformly disperse the hyperbranched polymer in a CSM matrix to form a pre-dispersed master batch; (3) Adding part of filler, grafted silane and initiator into the pre-dispersed master batch in the step (2), heating to 110-130 ℃, and reacting for 10-25 minutes under the protection of nitrogen, so that the grafted silane is grafted onto a CSM molecular chain to obtain a grafted master batch; (4) Compounding the multidimensional nano reinforced phase, namely cooling the grafting master batch in the step (3) to 80-100 ℃, adding the synergistically functionalized multidimensional nano reinforced phase and the crosslinking silane, and carrying out high-speed mixing for 8-15 minutes to uniformly disperse the nano material and carry out in-situ reaction; (5) Catalytic and final refining, namely cooling the mixture in the step (4) to below 60 ℃, adding a catalyst, an environment-friendly plasticizer, residual filler and functional auxiliary agents, uniformly carrying out thin-pass mixing on an open mill, and discharging tablets; (6) The molding and the program crosslinking are carried out, namely, the final rubber is manufactured into a product through extrusion, calendaring or compression molding, and a three-stage program crosslinking process is adopted, wherein the surface crosslinking is finished by firstly treating the final rubber at 80-90 ℃ and the relative humidity of 60-70% for 4-8 hours, then the final rubber is treated at 100-110 ℃ and the relative humidity of 80-90% for 8-16 hours, the bulk crosslinking is finished, and finally the final rubber is treated at 120-130 ℃ and the drying environment for 2-4 hours, and the final curing and the residual silanol condensation are finished.
  8. 8. The method for multi-dimensionally reinforced silane crosslinked chlorosulfonated polyethylene nanocomposite according to claim 7, wherein the ultrasonic power of the ultrasonic-assisted reaction in step (1) is 200-500W and the frequency is 20-40kHz, and the temperature, humidity and time of each stage in the three-stage procedure crosslinking process in step (6) can be optimally adjusted according to the thickness of the product, so as to satisfy the matching relationship between the thickness of the product and the crosslinking uniformity.
  9. 9. The method of claim 7, wherein the initiator is at least one of dicumyl peroxide, 1, 4-bis-tert-butylperoxy-isopropyl benzene or 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, and the addition amount of the initiator is 0.5-2.5% of the mass of the chlorosulfonated polyethylene.
  10. 10. Use of the multi-dimensional reinforced silane crosslinked chlorosulfonated polyethylene nanocomposite of any one of claims 1-6 in the preparation of nuclear power cable insulation, deep sea petroleum extraction equipment seals, new energy automobile high pressure connection systems, aerospace hydraulic seals or geothermal exploration equipment seals.

Description

Multidimensional reinforced silane crosslinked chlorosulfonated polyethylene nanocomposite and preparation method and application thereof Technical Field The invention relates to a multidimensional reinforced silane crosslinked chlorosulfonated polyethylene nanocomposite and a preparation method and application thereof, in particular to a silane crosslinked chlorosulfonated polyethylene nanocomposite based on a chemical grafting-nano reinforcing-topological entanglement triple network synergistic reinforcing mechanism and a preparation method thereof, and the application of the silane crosslinked chlorosulfonated polyethylene nanocomposite in high-end equipment for extreme environments, belonging to the technical field of high-performance special rubber composite materials. Background Chlorosulfonated polyethylene (CSM) is a special rubber prepared by chlorination and chlorosulfonation reaction of polyethylene, and the molecular chain of the special rubber contains chlorine atoms and sulfonyl chloride groups, so that the material is endowed with excellent weather resistance, ozone resistance, heat resistance and chemical medium resistance. Since the industrialization of DuPont 1952, CSM has been widely used in the fields of wire and cable, automotive industry, corrosion protection liners, etc. However, as the modern industry extends to extreme environments (high temperature, high pressure, strong corrosion, strong radiation), higher demands are placed on material properties. The traditional CSM cure system has the following challenges that are difficult to overcome: (1) Environmental protection defect of vulcanization system Conventional CSMs are mainly cured with metal oxides (especially lead oxide), organic peroxides or polyamines. Although the lead system has good vulcanizing effect, the lead system has large toxicity and is strictly limited by international environmental regulations such as RoHS, REACH and the like, the peroxide system is easy to cause scorching and sensitive to acid fillers, the processing window is narrow, and the polyamine system has poor storage stability and is easy to generate frosting. (2) Single cross-linked network structure The cross-linking network formed by the traditional vulcanization system takes C-C bond or metal ion coordination bond as the main component, has a single network structure, and is difficult to meet the requirement on the comprehensive performance of materials in a multi-field coupling service environment. In particular, under the synergistic effect of high temperature, high pressure and chemical medium, the traditional crosslinked network is easy to break, and the material is invalid. (3) Insufficient heat resistance level The long-term use temperature of the conventional CSM vulcanized rubber is generally not more than 125 ℃, and the requirement of the heat-resistant grade above 150 ℃ in the emerging fields of nuclear power, geothermal energy, deep sea and the like is difficult to meet. (4) Large compression set The cross-linked network formed by the traditional vulcanization system is uneven, and stress relaxation is easy to occur under a long-term compression state, so that the long-term reliability of the sealing element is affected. (5) Low filler reinforcing efficiency The interface combination of the conventional micron-sized filler and a CSM matrix is weak, the enhancement efficiency is limited, and the requirements of high strength and high wear resistance application are difficult to meet. The silane crosslinking technology is an environment-friendly crosslinking technology mature in the field of polyolefin materials, and forms a-Si-O-Si-three-dimensional network through silane grafting, hydrolytic condensation. In recent years, researchers have attempted to introduce this technique into CSM systems, such as that described in China patent application CN107851489A, which is directed to silane crosslinking techniques for halogen-containing polymers. However, the prior art mainly focuses on simple graft crosslinking of silane on CSM, and has the problems that (1) a crosslinked network structure is single, a multistage structural design is lacked, (2) the synergistic effect of a nano reinforcing phase and a silane network is not effectively utilized, (3) the heat-resistant grade is improved to a limited extent, and long-term use requirements above 150 ℃ are difficult to meet, and (4) the system consideration of a material failure mechanism under extreme environments is lacked. Aiming at the problems, the invention provides a brand-new chemical grafting-nano reinforcing-topological entanglement triple network cooperative reinforcing mechanism, and comprehensive breakthrough of the CSM composite material performance is realized through molecular design, nano-composite and topological structure regulation and control. Disclosure of Invention The invention aims to provide a multidimensional reinforced silane crosslinked chlorosulfonated polyethylene nano