CN112480505A - High-flame-retardant and aging-resistant air spring - Google Patents

High-flame-retardant and aging-resistant air spring Download PDF

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Publication number
CN112480505A
CN112480505A CN202011222410.2A CN202011222410A CN112480505A CN 112480505 A CN112480505 A CN 112480505A CN 202011222410 A CN202011222410 A CN 202011222410A CN 112480505 A CN112480505 A CN 112480505A
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parts
air spring
aging
carbon black
retardant
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CN112480505B (en
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余昌国
张先锋
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Anhui Hongqiao Metal Manufacturing Co Ltd
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Anhui Hongqiao Metal Manufacturing Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L11/00—Compositions of homopolymers or copolymers of chloroprene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/12—Layered products comprising a layer of natural or synthetic rubber comprising natural rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/16—Layered products comprising a layer of natural or synthetic rubber comprising polydienes homopolymers or poly-halodienes homopolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
    • F16F13/00—Units comprising springs of the non-fluid type as well as vibration-dampers, shock-absorbers, or fluid springs
    • F16F13/04—Units comprising springs of the non-fluid type as well as vibration-dampers, shock-absorbers, or fluid springs comprising both a plastics spring and a damper, e.g. a friction damper
    • F16F13/06—Units comprising springs of the non-fluid type as well as vibration-dampers, shock-absorbers, or fluid springs comprising both a plastics spring and a damper, e.g. a friction damper the damper being a fluid damper, e.g. the plastics spring not forming a part of the wall of the fluid chamber of the damper
    • F16F13/08—Units comprising springs of the non-fluid type as well as vibration-dampers, shock-absorbers, or fluid springs comprising both a plastics spring and a damper, e.g. a friction damper the damper being a fluid damper, e.g. the plastics spring not forming a part of the wall of the fluid chamber of the damper the plastics spring forming at least a part of the wall of the fluid chamber of the damper
    • F16F13/10—Units comprising springs of the non-fluid type as well as vibration-dampers, shock-absorbers, or fluid springs comprising both a plastics spring and a damper, e.g. a friction damper the damper being a fluid damper, e.g. the plastics spring not forming a part of the wall of the fluid chamber of the damper the plastics spring forming at least a part of the wall of the fluid chamber of the damper the wall being at least in part formed by a flexible membrane or the like
    • F16F13/103—Units comprising springs of the non-fluid type as well as vibration-dampers, shock-absorbers, or fluid springs comprising both a plastics spring and a damper, e.g. a friction damper the damper being a fluid damper, e.g. the plastics spring not forming a part of the wall of the fluid chamber of the damper the plastics spring forming at least a part of the wall of the fluid chamber of the damper the wall being at least in part formed by a flexible membrane or the like characterised by method of assembly, production or treatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
    • F16F13/00—Units comprising springs of the non-fluid type as well as vibration-dampers, shock-absorbers, or fluid springs
    • F16F13/04—Units comprising springs of the non-fluid type as well as vibration-dampers, shock-absorbers, or fluid springs comprising both a plastics spring and a damper, e.g. a friction damper
    • F16F13/06—Units comprising springs of the non-fluid type as well as vibration-dampers, shock-absorbers, or fluid springs comprising both a plastics spring and a damper, e.g. a friction damper the damper being a fluid damper, e.g. the plastics spring not forming a part of the wall of the fluid chamber of the damper
    • F16F13/08—Units comprising springs of the non-fluid type as well as vibration-dampers, shock-absorbers, or fluid springs comprising both a plastics spring and a damper, e.g. a friction damper the damper being a fluid damper, e.g. the plastics spring not forming a part of the wall of the fluid chamber of the damper the plastics spring forming at least a part of the wall of the fluid chamber of the damper
    • F16F13/10—Units comprising springs of the non-fluid type as well as vibration-dampers, shock-absorbers, or fluid springs comprising both a plastics spring and a damper, e.g. a friction damper the damper being a fluid damper, e.g. the plastics spring not forming a part of the wall of the fluid chamber of the damper the plastics spring forming at least a part of the wall of the fluid chamber of the damper the wall being at least in part formed by a flexible membrane or the like
    • F16F13/108—Units comprising springs of the non-fluid type as well as vibration-dampers, shock-absorbers, or fluid springs comprising both a plastics spring and a damper, e.g. a friction damper the damper being a fluid damper, e.g. the plastics spring not forming a part of the wall of the fluid chamber of the damper the plastics spring forming at least a part of the wall of the fluid chamber of the damper the wall being at least in part formed by a flexible membrane or the like characterised by features of plastics springs, e.g. attachment arrangements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Fireproofing Substances (AREA)

Abstract

The invention discloses a high-flame-retardant aging-resistant air spring, wherein a bag body of the air spring comprises an inner adhesive layer, a reinforcing layer and an outer adhesive layer from inside to outside; the raw materials of the outer glue layer comprise: chloroprene rubber, natural rubber, epichlorohydrin rubber, epoxidized natural rubber, polyaniline, carbon black, attapulgite, black shale powder, white carbon black, nano microcrystalline cellulose, a composite flame retardant, stearic acid, zinc oxide, magnesium oxide, sulfur, a promoter, an anti-aging agent 445, an anti-aging agent DDA, an anti-aging agent 2246, an anti-aging agent MB and a plasticizer; the composite flame retardant is a mixture of one or more of zinc sulfide, graphite-like carbon nitride, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, calcium borate, antimony trioxide, red phosphorus and aluminum hydroxide and ammonium polyphosphate, melamine cyanurate and lanthanum complex. The high-flame-retardant aging-resistant air spring provided by the invention has the advantages of excellent flame retardant property, good aging resistance and long service life.

Description

High-flame-retardant and aging-resistant air spring
Technical Field
The invention relates to the technical field of air springs, in particular to a high-flame-retardant and anti-aging air spring.
Background
The air spring is a curved capsule formed by sticking rubber and net wires, has the characteristics of light weight, good vibration isolation and noise elimination effects on high-frequency excitation vibration, high bearing capacity, nonlinear rigidity and the like, and is widely applied to the fields of automobiles, aviation, medical instruments, furniture, mechanical manufacturing and the like. The key part of the air spring is a rubber air bag which consists of an outer rubber layer, a reinforcing cord fabric layer and an inner rubber layer. The outer layer glue of the capsule body is a protective layer and is used for isolating external factors such as ozone, oxygen and the like from contacting with the cord fabric and preventing the cord fabric glue from aging. At present, natural rubber or chloroprene rubber is mostly adopted as outer layer rubber of a rubber capsule body, but the ozone resistance, the thermo-oxidative aging resistance and the flame retardance of the existing natural rubber and chloroprene rubber are still not ideal, and an air spring made of the natural rubber and chloroprene rubber is easy to crack in the long-term use process, so that the early failure of the product is finally caused, and the application of the air spring is limited.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides the high-flame-retardant aging-resistant air spring which is excellent in flame retardant property, good in aging resistance and long in service life.
The invention provides a high-flame-retardant aging-resistant air spring, wherein a bag body of the air spring comprises an inner adhesive layer, a reinforcing layer and an outer adhesive layer from inside to outside; the outer glue layer comprises the following raw materials in parts by weight: 65-80 parts of chloroprene rubber, 12-20 parts of natural rubber, 8-15 parts of epichlorohydrin rubber, 4-7.5 parts of epoxidized natural rubber, 1-3 parts of polyaniline, 8-15 parts of carbon black, 2-6 parts of attapulgite, 3-11 parts of black shale powder, 2-9 parts of white carbon black, 1-3 parts of nano microcrystalline cellulose, 20-38 parts of a composite flame retardant, 2-3 parts of stearic acid, 1-3 parts of zinc oxide, 1-5 parts of magnesium oxide, 1-2 parts of sulfur, 2-3 parts of a promoter, 4450.1-1 part of an anti-aging agent, 0.2-1.1 part of anti-aging agent DDA, 22460.1-1 part of anti-aging agent, 0.3-1.2 parts of anti-aging agent MB and 3-11 parts of a plasticizer;
the composite flame retardant is a mixture of one or more of zinc sulfide, graphite-like carbon nitride, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, calcium borate, antimony trioxide, red phosphorus and aluminum hydroxide and ammonium polyphosphate, melamine cyanurate and lanthanum complex.
Preferably, the epoxidized natural rubber has a molar content of epoxy groups of 20 to 32%.
Preferably, the carbon black is one or a mixture of more of carbon black N550, carbon black N990, carbon black N326, carbon black N774, carbon black N339 and carbon black N660.
Preferably, the promoter is one or a mixture of more of promoter DETU, promoter M, promoter NA-22, promoter TE and promoter ZIP.
Preferably, the plasticizer is one or a mixture of trioctyl phosphate, toluene diphenyl phosphate, dioctyl sebacate, dioctyl azelate, di-n-butyl sebacate, dibutyl maleate and phthalate.
Preferably, the plasticizer is dibutyl maleate, diphenyl cresyl phosphate and dioctyl sebacate in a weight ratio of 2-6: 3-9: 1-4.
Preferably, the composite flame retardant is a mixture of calcium borate, aluminum hydroxide, ammonium polyphosphate, melamine cyanurate and a lanthanum complex, and the weight ratio of the calcium borate to the aluminum hydroxide to the ammonium polyphosphate to the melamine cyanurate to the lanthanum complex is 2-7: 8-13: 9-15: 4-9: 1-5.
Preferably, the lanthanum complex is prepared according to the following process: adding 15-20 parts of naphthoic acid and 10-15 parts of isonicotinic acid into 500-1200 parts of dimethylacetamide by weight, adjusting the pH of the system to 6-7, adding 25-30 parts of lanthanum chloride, stirring at 55-65 ℃ for 10-20h, filtering, washing and drying to obtain the lanthanum complex.
Preferably, the magnesium oxide has a specific surface area of 200-300m2Magnesium oxide of/g, specific surface area of 130-170m2The weight ratio of magnesium oxide/g is 3-10: 1-3.
According to the high-flame-retardant anti-aging air spring, the outer rubber layer material of the air bag specifically takes chloroprene rubber as a main material, natural rubber and epichlorohydrin rubber are added for matching, epoxidized natural rubber is added as a compatilizer, the compatibility of the system is improved, the synergistic effect of the chloroprene rubber, the natural rubber and the epichlorohydrin rubber is exerted, the outer rubber is endowed with excellent aging resistance, oil resistance, heat resistance and cold resistance, and the defect that the pure chloroprene rubber is poor in low-temperature resistance is overcome; zinc oxide, magnesium oxide, sulfur and an accelerator are specifically selected as raw materials in a vulcanization system, and polyaniline is added, so that the crosslinking of rubber molecules in the system is promoted, the vulcanization speed is accelerated, the vulcanization time is shortened, the crosslinking density is improved, and the obtained material has excellent mechanical properties; the nano microcrystalline cellulose is added into the system and is matched with the carbon black, the attapulgite, the black shale powder and the white carbon black, so that the Payne effect of the system is weakened, the tensile strength, the heat aging resistance and the oil resistance of the outer rubber layer are improved, and the compression fatigue temperature rise and the compression permanent shape are reduced; one or more of zinc sulfide, graphite-like phase carbon nitride, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, calcium borate, antimony trioxide, red phosphorus and aluminum hydroxide is/are selected to be matched with a mixture of ammonium polyphosphate, melamine cyanurate and lanthanum complex to serve as a flame retardant, so that a synergistic effect is achieved, the heat release rate and the total heat release amount are reduced on the basis of not reducing the mechanical property of the material, the residual carbon amount of the system is increased, the smoke density is reduced, and the flame-retardant and smoke-suppression effects are excellent; the lanthanum complex specifically uses naphthoic acid and isonicotinic acid as ligands, uses lanthanum chloride as metal salt, and is added into a flame retardant, so that the complex and the generated ligand can promote decomposition of ammonium polyphosphate and the like at high temperature, inhibit combustion, reduce weight loss, improve the flame retardant effect of outer layer glue, and simultaneously are matched with an anti-aging agent 445, an anti-aging agent DDA, an anti-aging agent 2246, an anti-aging agent MB and the like, so that the aging resistance of the material is improved.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
The invention provides a high-flame-retardant aging-resistant air spring, wherein a bag body of the air spring comprises an inner adhesive layer, a reinforcing layer and an outer adhesive layer from inside to outside; the outer glue layer comprises the following raw materials in parts by weight: 80 parts of chloroprene rubber, 12 parts of natural rubber, 8 parts of epichlorohydrin rubber, 7.5 parts of epoxidized natural rubber, 1 part of polyaniline, 15 parts of carbon black, 2 parts of attapulgite, 3 parts of black shale powder, 9 parts of white carbon black, 1 part of nano microcrystalline cellulose, 38 parts of a composite flame retardant, 3 parts of stearic acid, 3 parts of zinc oxide, 1 part of magnesium oxide, 2 parts of sulfur, 2 parts of a promoter, 4451 parts of an anti-aging agent, 0.2 part of an anti-aging agent DDA, 22461 parts of the anti-aging agent MB 0.3 part and 11 parts of a plasticizer;
the composite flame retardant is a mixture of zinc sulfide, ammonium polyphosphate, melamine cyanurate and a lanthanum complex; and the weight ratio of the zinc sulfide to the ammonium polyphosphate, the melamine cyanurate and the lanthanum complex is 1: 5: 1: 0.3.
example 2
The invention provides a high-flame-retardant aging-resistant air spring, wherein a bag body of the air spring comprises an inner adhesive layer, a reinforcing layer and an outer adhesive layer from inside to outside; the outer glue layer comprises the following raw materials in parts by weight: 65 parts of chloroprene rubber, 20 parts of natural rubber, 15 parts of epichlorohydrin rubber, 4 parts of epoxidized natural rubber, 3 parts of polyaniline, 8 parts of carbon black, 4 parts of attapulgite, 11 parts of black shale powder, 2 parts of white carbon black, 3 parts of nano microcrystalline cellulose, 28 parts of a composite flame retardant, 2 parts of stearic acid, 1.8 parts of zinc oxide, 5 parts of magnesium oxide, 1 part of sulfur, 3 parts of an accelerator, 4450.1 parts of an anti-aging agent, 1.1 parts of an anti-aging agent DDA, 22460.1 parts of an anti-aging agent MB 1 part and 3 parts of a plasticizer;
the composite flame retardant is a mixture of antimony trioxide, aluminum hydroxide, ammonium polyphosphate, melamine cyanurate and a lanthanum complex, and the weight ratio of the antimony trioxide to the aluminum hydroxide to the ammonium polyphosphate to the melamine cyanurate to the lanthanum complex is 1: 5: 9: 7: 1.
example 3
The invention provides a high-flame-retardant aging-resistant air spring, wherein a bag body of the air spring comprises an inner adhesive layer, a reinforcing layer and an outer adhesive layer from inside to outside; the outer glue layer comprises the following raw materials in parts by weight: 72 parts of chloroprene rubber, 15 parts of natural rubber, 13 parts of epichlorohydrin rubber, 4.1 parts of epoxidized natural rubber, 2 parts of polyaniline, 5 parts of carbon black N5509 parts, 6 parts of attapulgite, 6 parts of black shale powder, 7 parts of white carbon black, 1.2 parts of nano microcrystalline cellulose, 20 parts of a composite flame retardant, 2.2 parts of stearic acid, 1 part of zinc oxide, 2 parts of magnesium oxide, 1.4 parts of sulfur, 2.6 parts of an accelerator DETU, 4450.6 parts of an anti-aging agent, 0.7 part of an anti-aging agent DDA, 22460.8 parts of the anti-aging agent, 1.2 parts of an anti-aging agent MB and 9 parts of trioctyl phosphate;
the composite flame retardant is a mixture of zinc sulfide, calcium borate, red phosphorus, ammonium polyphosphate, melamine cyanurate and a lanthanum complex, and the weight ratio of the zinc sulfide, the calcium borate, the red phosphorus, the ammonium polyphosphate, the melamine cyanurate and the lanthanum complex is 0.5: 3: 7: 9: 9: 1;
the lanthanum complex is prepared according to the following process: adding 15 parts of naphthoic acid and 15 parts of isonicotinic acid into 500 parts of dimethylacetamide according to parts by weight, adjusting the pH of the system to be 7, adding 25 parts of lanthanum chloride, stirring for 10 hours at 65 ℃, filtering, washing and drying to obtain the lanthanum complex;
the magnesium oxide has a specific surface area of 200m2Magnesium oxide in a specific surface area of 170 m/g2The weight ratio of magnesium oxide to magnesium oxide is 3: 3 in a mixture of two or more.
Example 4
The invention provides a high-flame-retardant aging-resistant air spring, wherein a bag body of the air spring comprises an inner adhesive layer, a reinforcing layer and an outer adhesive layer from inside to outside; the outer glue layer comprises the following raw materials in parts by weight: 69 parts of chloroprene rubber, 18 parts of natural rubber, 13 parts of epichlorohydrin rubber, 7 parts of epoxidized natural rubber, 1.8 parts of polyaniline, 9907 parts of carbon black N, 7745 parts of carbon black N, 3 parts of attapulgite, 9.2 parts of black shale powder, 4.1 parts of white carbon black, 2.7 parts of nano microcrystalline cellulose, 26 parts of a composite flame retardant, 2.5 parts of stearic acid, 1.3 parts of zinc oxide, 4 parts of magnesium oxide, 1 part of sulfur, 1 parts of a promoter M, NA-221 parts of a promoter, ZIP 1 part of a promoter, 4450.1 parts of an anti-aging agent, DDA 1 part, 22460.1 parts of the anti-aging agent, 0.7 part of the anti-aging agent MB, 2 parts of diphenyl cresyl phosphate and 2.3 parts of dioctyl azelate;
wherein, in the epoxidized natural rubber, the molar content of the epoxy group is 20 percent;
the composite flame retardant is a mixture of calcium borate, aluminum hydroxide, ammonium polyphosphate, melamine cyanurate and a lanthanum complex, and the weight ratio of the calcium borate to the aluminum hydroxide to the ammonium polyphosphate to the melamine cyanurate to the lanthanum complex is 7: 8: 15: 4: 5;
the lanthanum complex is prepared according to the following process: adding 20 parts by weight of naphthoic acid and 10 parts by weight of isonicotinic acid into 1200 parts by weight of dimethylacetamide, adjusting the pH of the system to 6, adding 30 parts by weight of lanthanum chloride, stirring at 55 ℃ for 20 hours, filtering, washing and drying to obtain the lanthanum complex;
the magnesium oxide has a specific surface area of 300m2Magnesium oxide in a specific surface area of 130 m/g2The weight ratio of magnesium oxide to magnesium oxide is 10: 1.
Example 5
The invention provides a high-flame-retardant aging-resistant air spring, wherein a bag body of the air spring comprises an inner adhesive layer, a reinforcing layer and an outer adhesive layer from inside to outside; the outer glue layer comprises the following raw materials in parts by weight: 69 parts of chloroprene rubber, 17 parts of natural rubber, 14 parts of epichlorohydrin rubber, 7.1 parts of epoxidized natural rubber, 2.6 parts of polyaniline, N5505 parts of carbon black, N3262 parts of carbon black, N3395 parts of carbon black, 5.1 parts of attapulgite, 7 parts of black shale powder, 7 parts of white carbon black, 1 part of nano microcrystalline cellulose, 29 parts of composite flame retardant, 2.2 parts of stearic acid, 1.5 parts of zinc oxide, 2 parts of magnesium oxide, 1.7 parts of sulfur, 0.3 part of accelerator M1, 0.7 part of accelerator TE, 0.7 part of accelerator ZIP, 4450.7 parts of antioxidant, 0.5 part of antioxidant DDA, 22460.6 parts of antioxidant, 0.6 part of antioxidant MB and 8 parts of plasticizer;
wherein, in the epoxidized natural rubber, the molar content of the epoxy group is 32 percent;
the plasticizer is dibutyl maleate, diphenyl toluate phosphate and dioctyl sebacate in a weight ratio of 3: 4: 2;
the composite flame retardant is a mixture of calcium borate, aluminum hydroxide, ammonium polyphosphate, melamine cyanurate and a lanthanum complex, and the weight ratio of the calcium borate to the aluminum hydroxide to the ammonium polyphosphate to the melamine cyanurate to the lanthanum complex is 2: 13: 9: 9: 1;
the lanthanum complex is prepared according to the following process: adding 17 parts of naphthoic acid and 14 parts of isonicotinic acid in 800 parts of dimethylacetamide according to parts by weight, adjusting the pH of the system to be 7, adding 27 parts of lanthanum chloride, stirring for 13 hours at 60 ℃, filtering, washing and drying to obtain the lanthanum complex;
the magnesium oxide has a specific surface area of 200-300m2Magnesium oxide of/g, specific surface area of 130-170m2The weight ratio of magnesium oxide to magnesium oxide is 6: 1.
Example 6
The invention provides a high-flame-retardant aging-resistant air spring, wherein a bag body of the air spring comprises an inner adhesive layer, a reinforcing layer and an outer adhesive layer from inside to outside; the outer glue layer comprises the following raw materials in parts by weight: 75 parts of chloroprene rubber, 15 parts of natural rubber, 10 parts of epichlorohydrin rubber, 6 parts of epoxidized natural rubber, 2 parts of polyaniline, N5503 parts of carbon black, N9903 parts of carbon black, N6604 parts of carbon black, 4 parts of attapulgite, 9 parts of black shale powder, 5 parts of white carbon black, 2 parts of nano microcrystalline cellulose, 32 parts of a composite flame retardant, 2.5 parts of stearic acid, 2 parts of zinc oxide, 3.2 parts of magnesium oxide, 1 part of sulfur, 1 parts of a promoter M, NA-221.6 parts of a promoter, 4450.3 parts of an anti-aging agent, DDA 1 parts, 22461 parts of the anti-aging agent, MB 1 part of the anti-aging agent and 7 parts of a plasticizer;
wherein, in the epoxidized natural rubber, the molar content of the epoxy group is 26 percent;
the plasticizer is dibutyl maleate, diphenyl toluate phosphate and dioctyl sebacate in a weight ratio of 6: 7: 3;
the composite flame retardant is a mixture of calcium borate, aluminum hydroxide, ammonium polyphosphate, melamine cyanurate and a lanthanum complex, and the weight ratio of the calcium borate to the aluminum hydroxide to the ammonium polyphosphate to the melamine cyanurate to the lanthanum complex is 6: 9: 11: 5: 3;
the lanthanum complex is prepared according to the following process: adding 18 parts by weight of naphthoic acid and 12 parts by weight of isonicotinic acid into 1000 parts by weight of dimethylacetamide, adjusting the pH of the system to be 6, adding 30 parts by weight of lanthanum chloride, stirring for 17 hours at 58 ℃, filtering, washing and drying to obtain the lanthanum complex.
The performance of the outer rubber layer material of the capsule of the high-flame-retardant and aging-resistant air spring in the embodiments 4 to 6 of the invention is detected, and the detection results are as follows: the tensile strength is 17.3-18.7MPa (GB/T528-; the maximum average heat release rate is 12.4-13.9kw/m2(ISO 5659-2); oil resistance (IRM902 oil, 70 ℃ multiplied by 72h), and the weight change per unit area of 107-2(GB/T1690); dynamic ozone resistance (50pphm, 40 ℃, 168h, 0-20% stretching and 0.5Hz frequency) and no crack (GB/T13642); the thermal aging resistance test (80 ℃, 1000h) shows that the tensile strength change rate is 0.7-1.2 percent and the elongation at break change rate is 1.4-2.0 percent; smoke density, Ds 207-211(EN 45545-2); the limiting oxygen index is more than or equal to 39 percent (GB/T10707-2008).
Comparative example 1
The only difference from example 6 is that: the composite flame retardant does not contain lanthanum complex.
Comparative example 2
The only difference from example 6 is that: the composite flame retardant does not contain calcium borate.
Comparative example 3
The only difference from example 6 is that: the composite flame retardant does not contain aluminum hydroxide.
Comparative example 4
The only difference from example 6 is that: the composite flame retardant does not contain aluminum hydroxide and calcium borate.
Comparative example 5
The only difference from example 6 is that: the composite flame retardant does not contain ammonium polyphosphate.
Comparative example 6
The only difference from example 6 is that: the composite flame retardant does not contain melamine cyanurate.
Comparative example 7
The only difference from example 6 is that: the composite flame retardant does not contain ammonium polyphosphate, melamine cyanurate and lanthanum complex.
The flame retardant property of the outer rubber layer material in the comparative examples 1 to 7 is detected, and the maximum average heat release rate is more than or equal to 21.6kw/m2(ISO 5659-2); the smoke density is equal to or more than 268(EN45545-2) for Ds; the limiting oxygen index is 31-35% (GB/T10707-2008); meanwhile, the aging resistance of the middle and outer glue line material in the comparative example 1 is detected, and the tensile strength change rate is-1.7% and the elongation at break change rate is-2.8% after the thermal aging resistance test (80 ℃, 1000 h).
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (9)

1. A high flame-retardant aging-resistant air spring is characterized in that a bag body of the air spring comprises an inner adhesive layer, a reinforcing layer and an outer adhesive layer from inside to outside; the outer glue layer comprises the following raw materials in parts by weight: 65-80 parts of chloroprene rubber, 12-20 parts of natural rubber, 8-15 parts of epichlorohydrin rubber, 4-7.5 parts of epoxidized natural rubber, 1-3 parts of polyaniline, 8-15 parts of carbon black, 2-6 parts of attapulgite, 3-11 parts of black shale powder, 2-9 parts of white carbon black, 1-3 parts of nano microcrystalline cellulose, 20-38 parts of a composite flame retardant, 2-3 parts of stearic acid, 1-3 parts of zinc oxide, 1-5 parts of magnesium oxide, 1-2 parts of sulfur, 2-3 parts of a promoter, 4450.1-1 part of an anti-aging agent, 0.2-1.1 part of anti-aging agent DDA, 22460.1-1 part of anti-aging agent, 0.3-1.2 parts of anti-aging agent MB and 3-11 parts of a plasticizer;
the composite flame retardant is a mixture of one or more of zinc sulfide, graphite-like carbon nitride, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, calcium borate, antimony trioxide, red phosphorus and aluminum hydroxide and ammonium polyphosphate, melamine cyanurate and lanthanum complex.
2. The air spring with high flame retardance and aging resistance as claimed in claim 1, wherein the epoxidized natural rubber has an epoxy group content of 20-32 mol%.
3. The air spring with high flame retardance and aging resistance as claimed in claim 1, wherein the carbon black is one or a mixture of carbon black N550, carbon black N990, carbon black N326, carbon black N774, carbon black N339 and carbon black N660.
4. The air spring with high flame retardance and aging resistance as claimed in claim 1, wherein the accelerant is one or a mixture of accelerant DETU, accelerant M, accelerant NA-22, accelerant TE and accelerant ZIP.
5. The air spring of claim 1, wherein the plasticizer is one or more selected from the group consisting of trioctyl phosphate, cresyldiphenyl phosphate, dioctyl sebacate, dioctyl azelate, di-n-butyl sebacate, dibutyl maleate, and phthalate.
6. The air spring with high flame retardance and aging resistance as claimed in claim 5, wherein the plasticizer is dibutyl maleate, diphenyl cresyl phosphate and dioctyl sebacate in a weight ratio of (2-6): 3-9: 1-4.
7. The air spring with high flame retardance and aging resistance as claimed in claim 1, wherein the composite flame retardant is a mixture of calcium borate, aluminum hydroxide, ammonium polyphosphate, melamine cyanurate and lanthanum complex, and the weight ratio of the calcium borate to the aluminum hydroxide to the ammonium polyphosphate to the melamine cyanurate to the lanthanum complex is 2-7: 8-13: 9-15: 4-9: 1-5.
8. The high-flame-retardant aging-resistant air spring according to claim 1, wherein the lanthanum complex is prepared by the following process: adding 15-20 parts of naphthoic acid and 10-15 parts of isonicotinic acid into 500-1200 parts of dimethylacetamide by weight, adjusting the pH of the system to 6-7, adding 25-30 parts of lanthanum chloride, stirring at 55-65 ℃ for 10-20h, filtering, washing and drying to obtain the lanthanum complex.
9. The air spring with high flame retardance and aging resistance as claimed in any one of claims 1 to 8, wherein the magnesium oxide has a specific surface area of 200-300m2Magnesium oxide of/g, specific surface area of 130-170m2The weight ratio of magnesium oxide/g is 3-10: 1-3.
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