CN117050402B - Sound-insulating and shock-absorbing rubber composite material and preparation method thereof - Google Patents

Sound-insulating and shock-absorbing rubber composite material and preparation method thereof Download PDF

Info

Publication number
CN117050402B
CN117050402B CN202311317105.5A CN202311317105A CN117050402B CN 117050402 B CN117050402 B CN 117050402B CN 202311317105 A CN202311317105 A CN 202311317105A CN 117050402 B CN117050402 B CN 117050402B
Authority
CN
China
Prior art keywords
rubber
parts
carbon nano
composite material
nano tube
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202311317105.5A
Other languages
Chinese (zh)
Other versions
CN117050402A (en
Inventor
水野晃辅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Iida Foshan Industry Co ltd
Original Assignee
Iida Foshan Industry Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Iida Foshan Industry Co ltd filed Critical Iida Foshan Industry Co ltd
Priority to CN202311317105.5A priority Critical patent/CN117050402B/en
Publication of CN117050402A publication Critical patent/CN117050402A/en
Application granted granted Critical
Publication of CN117050402B publication Critical patent/CN117050402B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02Copolymers with acrylonitrile
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2296Oxides; Hydroxides of metals of zinc
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/80Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86Optimisation of rolling resistance, e.g. weight reduction 

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to the technical field of compositions of high molecular compounds, and particularly discloses a sound-insulating and shock-absorbing rubber composite material and a preparation method thereof. The rubber composite material comprises the following raw materials in parts by weight: 35-70 parts of nitrile rubber, 5-25 parts of butyl rubber, 5-25 parts of ethylene propylene diene monomer, 2-8 parts of carbon black, 1-2.5 parts of an anti-aging agent, 0.5-1.5 parts of an accelerator, 2-5 parts of a vulcanizing agent, 2-8 parts of zinc oxide, 1-3 parts of stearic acid and 2-5 parts of a modified carbon nano tube. The invention also provides a preparation method of the composite. Compared with the prior art, the rubber composite material prepared by the invention not only has better damping performance, but also has good mechanical property and thermal aging resistance, and is very suitable for being applied to the field of automobiles.

Description

Sound-insulating and shock-absorbing rubber composite material and preparation method thereof
Technical Field
The invention relates to the technical field of compositions of high molecular compounds, in particular to a sound-insulating and shock-absorbing rubber composite material and a preparation method thereof.
Background
With the rapid development of high performance technology in the automobile manufacturing industry, the development of automobile technology has been to achieve economical use of automobiles and to improve comfort and safety of automobiles. This places higher demands on the rubber damping element from the standpoint of damping, noise, comfort and driving stability. The vibration phenomenon of an automobile is quite complex, and the most obvious vibration is the natural vibration of the sprung mass supported by the suspension spring arrangement. Therefore, the damping rubber product is mainly used for controlling vibration and noise of the automobile and improving the steering stability of the automobile, and is generally arranged at the positions of an automobile frame, a compression bar device, a suspension bushing, a central bearing bracket, a bump limiter, a torsional vibration damper and the like so as to improve the safety and the comfort of the automobile.
The rubber used for vibration damping is of various types, mainly natural rubber and styrene-butadiene rubber, and nitrile rubber (NBR), chloroprene Rubber (CR), butyl rubber (IR), ethylene Propylene Diene Monomer (EPDM) and the like are also used for improving the heat resistance of vibration damping products. Different rubber materials are usually selected or several rubbers are blended and certain modification methods are adopted to improve certain property and properties of the rubber materials according to different application environments and use requirements.
Chinese patent 201910637212.3 discloses a foaming rubber composition and vulcanized rubber based on ethylene propylene diene monomer rubber, and a preparation method and application thereof, wherein the composition comprises a rubber matrix, a filler, a vulcanizing agent, a vulcanization accelerator, an activating agent, a foaming agent and a foaming aid, the rubber matrix comprises nitrile rubber, polyvinyl chloride and ethylene propylene diene monomer rubber, the content of the ethylene propylene diene monomer rubber is 10-30 parts by weight relative to 100 parts by weight of the nitrile rubber and the polyvinyl chloride, and the content weight ratio of the nitrile rubber to the polyvinyl chloride is (1-9): 1. the foaming material prepared from the foaming rubber composition has high aperture ratio, good low-temperature performance and good tensile strength, and is particularly suitable for the fields of electric automobiles and the like to prepare the damping and sound-insulating foaming material.
Chinese patent 201710873535.3 discloses a method for preparing a damping and noise reducing rubber nanocomposite device, which comprises the following steps: modified carbon nano tube, nano white carbon black, anti-aging agent, accelerator, kaolin, plasticizer, rare earth complex and Al 2 O 3 Micropowder, si 3 N 4 Micro powder and TiO 2 Adding the micropowder and polytetrafluoroethylene micropowder into a high-speed stirrer, stirring and mixing to obtain a mixture; adding butyl rubber, nitrile rubber, ethylene propylene diene monomer rubber and a mixture into an internal mixer for mixing, cooling, adding the cooled mixed primary material, modified graphene oxide, zinc oxide, a vulcanizing agent and stearic acid into an open mill, and carrying out thin pass to obtain a mixed material; adding the mixed materials into an ultrasonic extrusion integrated device, extruding, and vulcanizing to obtain a noise-reducing and shock-absorbing rubber nanocomposite device; the device prepared by the invention has excellent mechanical property and noise reduction and vibration absorption performance, the tensile strength of the composite material is more than or equal to 18MPa, the elongation at break is more than or equal to 400%, and the tearing strength is more than or equal to 45 KN.m -1 The method comprises the steps of carrying out a first treatment on the surface of the Compression set of 100 ℃ multiplied by 72h multiplied by 25 percent is less than or equal to 22 percent.
In the prior art, the compounding modification of rubber is mostly carried out in a mode of adding filler, and the characteristics of high strength, high thermal conductivity or high electrical conductivity of the filler bring about performance improvement to the material, but the characteristics of easy agglomeration and incompatibility with the polymer of the filler can influence the final performance of the material, so that the modification of the filler to improve the dispersibility and interface bonding property are very important to the rubber material.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides a sound-insulating and shock-absorbing rubber composite material and a method for preparing the same, which can solve at least one of the above-mentioned technical problems.
The rubber has large-volume side groups or a plurality of side groups in a molecular structure, so that the steric hindrance of the rubber is increased, the flexibility of a molecular chain is reduced, the movement capacity is limited, the intramolecular friction is increased, the damping performance is good, the vibration and noise of the structure can be reduced, and the mechanical environment is improved. However, the damping rubber material has good damping and vibration reduction performance and effective damping temperature range only in a low-temperature glass transition region, but cannot meet the requirements of use at normal temperature and higher temperature. Therefore, the rubber needs to be subjected to composite modification, so that the damping effect and the damping temperature range of the rubber in the environment temperature range can be improved, and other performances can be improved.
In the invention, the inventor obtains the modified carbon nano tube by reacting carboxylated carbon nano tube with 3- (4-aminophenyl) -1, 2-propylene glycol, wherein 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is used as an activating agent with active imine to activate the carboxylated carbon nano tube to obtain active ester, the active ester has electrophilicity and 4-dimethylaminopyridine to form a compound, which is favorable for nucleophilic addition reaction, 4-dimethylaminopyridine can also catalyze reaction by being used as a catalyst, and finally the modified carbon nano tube is obtained through post-treatment. Interactions between the modified carbon nanotubes are weakened, so that agglomeration is less likely to occur. Because the carbon nano tube has extremely high strength and height and good heat conducting performance, the carbon nano tube is mixed with raw materials such as nitrile rubber and the like, not only can the rigidity of a rubber material be improved, but also the carbon nano tube has small particle size and large specific surface area, can generate strong interface action when being compounded with the rubber material, and can generate bonding-sliding process under an external dynamic force field, so that interface friction is generated, the damping performance of the material is improved, the damping effect of the material is better, and the damping temperature range of the material can be enlarged.
In order to achieve the above purpose, the invention provides a sound-insulating and shock-absorbing rubber composite material, which comprises the following raw materials in parts by weight: 35-70 parts of nitrile rubber, 5-25 parts of butyl rubber, 5-25 parts of ethylene propylene diene monomer, 2-8 parts of carbon black, 1-2.5 parts of an anti-aging agent, 0.5-1.5 parts of an accelerator, 2-5 parts of a vulcanizing agent, 2-8 parts of zinc oxide, 1-3 parts of stearic acid and 2-5 parts of a modified carbon nano tube.
Further, the anti-aging agent is one or more than two of N- (1, 3-dimethyl, butyl) -N-phenyl p-phenylenediamine, N-di-N-butyl dithiocarbamic acid nickel and 2, 4-trimethyl-1, 2-dihydroquinoline polymer.
Further, the accelerator is one or more than two of tetramethylthiuram disulfide, ethylene thiourea and alkylated triethylenetetramine thiuram disulfide.
Further, the vulcanizing agent is sulfur.
Preferably, the anti-aging agent is prepared by mixing N- (1, 3-dimethyl, butyl) -N-phenyl-p-phenylenediamine, N-di-N-butyl-dithiocarbamic acid nickel and 2, 4-trimethyl-1, 2-dihydroquinoline polymer according to the mass ratio of 0.5-1:0.5-1:0.1-0.5.
Preferably, the accelerator is prepared from 0.4-0.8 of ethylene thiourea and alkylated triethylenetetramine thiuram disulfide: and mixing the materials according to a mass ratio of 0.1-0.5.
The preparation method of the modified carbon nano tube comprises the following steps:
s1, adding 2-5 parts by weight of carboxylated carbon nanotubes and 5-15 parts by weight of 3- (4-aminophenyl) -1, 2-propanediol into 100-500 parts by weight of N, N-dimethylformamide, and then adding 0.5-1.5 parts by weight of 4-dimethylaminopyridine, and uniformly dispersing to obtain a solution A;
s2, adding 4-10 parts by weight of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride into 50-100 parts by weight of N, N-dimethylformamide, uniformly stirring to obtain a solution B, cooling the solution A to 0-5 ℃, adding the solution B into the solution A under a nitrogen atmosphere, stirring for 12-24 hours, filtering, and centrifuging the residue after acid washing, alkali washing, brine washing and water washing, and drying to obtain the modified carbon nanotube.
A preparation method of a sound-insulating and shock-absorbing rubber composite material comprises the following steps:
mixing nitrile rubber, butyl rubber, ethylene propylene diene monomer, carbon black, an anti-aging agent and an accelerator, banburying at 90-120 ℃, mixing the mixture with modified carbon nano tubes, a vulcanizing agent, zinc oxide and stearic acid for open milling after 50-80 min, extruding after 4-8 times of thin pass, and vulcanizing at 130-160 ℃ and 10-20 MPa for 20-30 min to obtain the sound insulation and shock absorption rubber composite material.
The material performance can be improved in multiple directions by taking the nitrile rubber, the butyl rubber and the ethylene propylene diene monomer rubber as raw materials for blending, the carbon black can reduce material defects and delay fatigue process as a high-structure material, the effect of the anti-aging agent is to inhibit oxidation and aging phenomena caused by heat, light and the like, the effect of the accelerator is to shorten the vulcanization time and reduce the vulcanization temperature, and the effect of the zinc oxide and the stearic acid in the rubber is to activate a system, so that the crosslinking density can be improved and the vulcanization can be promoted. The modified carbon nano tube is added, so that the damping performance of the material can be improved, a better damping effect can be achieved, the damping temperature range of the material can be enlarged, and finally the purposes of improving damping, reducing noise and resisting heat aging are achieved.
The invention has the beneficial effects that:
1. the dispersibility and compatibility of the carbon nano tube in the rubber material are improved by modifying the carbon nano tube, and the modified carbon nano tube is added into the rubber composite material, so that the damping performance is improved, and the damping effect and the damping temperature range of the carbon nano tube in the environment temperature range can be improved
2. Compared with the prior art, the rubber composite material provided by the invention has good damping performance, good mechanical property and thermal aging resistance, and is very suitable for being applied to the field of automobiles.
Detailed Description
Nitrile rubber, trademark 3345, guangzhou market force rubber raw material.
Butyl rubber, brand 1751, yanshan petrochemical.
Ethylene propylene diene monomer, brand 4045M, shanghai Sanjing.
Carbon black, model N330.
3- (4-aminophenyl) -1, 2-propanediol, 3- (4-aminophenyl) propane-1,2-diol, CAS number: 182919-17-1.
Carboxylated carbon nanotubes with the particle size of 10-20 nm and the length of 10-30 μm are prepared by the biotechnology of Siemens Ji Yue.
Comparative example 1
A preparation method of a sound-insulating and shock-absorbing rubber composite material comprises the following steps:
55g of nitrile rubber, 15g of butyl rubber, 15g of ethylene propylene diene monomer, 5g of carbon black, 0.75g of N- (1, 3-dimethyl, butyl) -N-phenyl p-phenylenediamine, 0.75g of nickel N, N-di-N-butyl dithiocarbamic acid, 0.3g of 2, 4-trimethyl-1, 2-dihydroquinoline polymer, 0.75g of ethylene-propylene-diene thiourea and 0.25g of alkylated triethylenetetramine thiuram disulfide are mixed and banburying is carried out at 110 ℃, the rotating speed is 75rpm,60min, the mixture is mixed and banburying is carried out with 3g of carboxylated carbon nano tube, 4.5g of sulfur, 5g of zinc oxide and 3g of stearic acid after 8 times of thin pass, extrusion is carried out, and vulcanization is carried out for 30min under 15MPa at 150 ℃, thus obtaining the sound insulation and shock absorption rubber composite material.
Example 1
A preparation method of a sound-insulating and shock-absorbing rubber composite material comprises the following steps:
55g of nitrile rubber, 15g of butyl rubber, 15g of ethylene propylene diene monomer, 5g of carbon black, 0.75g of N- (1, 3-dimethyl, butyl) -N-phenyl p-phenylenediamine, 0.75g of N, N-di-N-butyl dithiocarbamic acid nickel, 0.3g of 2, 4-trimethyl-1, 2-dihydroquinoline polymer, 0.75g of ethylene-propylene-diene thiourea and 0.25g of alkylated triethylenetetramine thiuram disulfide are mixed and banburying is carried out at 110 ℃, the rotating speed is 75rpm,60min, the mixture is mixed and banburying is carried out with 3g of modified carbon nano tube, 4.5g of sulfur, 5g of zinc oxide and 3g of stearic acid after 8 times of thin pass, and then extrusion is carried out, and vulcanization is carried out for 30min under 15MPa at 150 ℃, thus obtaining the sound insulation and shock absorption rubber composite material.
The preparation method of the modified carbon nano tube comprises the following steps:
s1, adding 3g of carboxylated carbon nano tubes and 7.5g of 3- (4-aminophenyl) -1, 2-propanediol into 500mL of N, N-dimethylformamide, adding 0.6g of 4-dimethylaminopyridine, and uniformly dispersing to obtain a solution A;
s2, adding 6g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride into 60mL of N, N-dimethylformamide, stirring uniformly to obtain a solution B, cooling the solution A to 0 ℃, adding the solution B into the solution A under nitrogen atmosphere, stirring for 16 hours, filtering, centrifuging the residue for 10 minutes at 8500rpm after acid washing, alkali washing, brine washing and water washing, and drying the lower precipitate at 80 ℃ for 6 hours to obtain the modified carbon nanotube.
Example 2
A preparation method of a sound-insulating and shock-absorbing rubber composite material comprises the following steps:
55g of nitrile rubber, 15g of butyl rubber, 15g of ethylene propylene diene monomer, 5g of carbon black, 0.75g of N- (1, 3-dimethyl, butyl) -N-phenyl p-phenylenediamine, 0.75g of N, N-di-N-butyl dithiocarbamic acid nickel, 0.3g of 2, 4-trimethyl-1, 2-dihydroquinoline polymer, 0.75g of ethylene-propylene-diene thiourea and 0.25g of alkylated triethylenetetramine thiuram disulfide are mixed and banburying is carried out at 110 ℃, the rotating speed is 75rpm,60min, the mixture is mixed and banburying is carried out with 3g of modified carbon nano tube, 4.5g of sulfur, 5g of zinc oxide and 3g of stearic acid after 8 times of thin pass, and then extrusion is carried out, and vulcanization is carried out for 30min under 15MPa at 150 ℃, thus obtaining the sound insulation and shock absorption rubber composite material.
The preparation method of the modified carbon nano tube comprises the following steps:
adding 3g of carboxylated carbon nano tube into 1L of water, uniformly dispersing, adding 2g of dopamine hydrochloride, uniformly stirring and dispersing, adding 1mol/L Tris buffer solution to adjust the pH to 8.5, heating to 60 ℃, stirring for 8 hours, filtering, washing residues with water for three times, centrifuging at 8500rpm for 10 minutes, and drying the lower precipitate at 80 ℃ for 6 hours to obtain the modified carbon nano tube.
Example 3
A preparation method of a sound-insulating and shock-absorbing rubber composite material comprises the following steps:
55g of nitrile rubber, 15g of butyl rubber, 15g of ethylene propylene diene monomer, 8g of carbon black, 0.75g of N- (1, 3-dimethyl, butyl) -N-phenyl p-phenylenediamine, 0.75g of N, N-di-N-butyl dithiocarbamic acid nickel, 0.3g of 2, 4-trimethyl-1, 2-dihydroquinoline polymer, 0.75g of ethylene-propylene-diene thiourea and 0.25g of alkylated triethylenetetramine thiuram disulfide are mixed and banburying is carried out at 110 ℃, the rotating speed is 75rpm,60min, the mixture is mixed and banburying is carried out with 3g of modified carbon nano tube, 4.5g of sulfur, 5g of zinc oxide and 3g of stearic acid after 8 times of thin pass, and then extrusion is carried out, and vulcanization is carried out for 30min under 15MPa at 150 ℃, thus obtaining the sound insulation and shock absorption rubber composite material.
The preparation method of the modified carbon nano tube comprises the following steps:
s1, adding 3g of carboxylated carbon nano tubes and 7.5g of 3- (4-aminophenyl) -1, 2-propanediol into 500mL of N, N-dimethylformamide, adding 0.6g of 4-dimethylaminopyridine, and uniformly dispersing to obtain a solution A;
s2, adding 6g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride into 60mL of N, N-dimethylformamide, stirring uniformly to obtain a solution B, cooling the solution A to 0 ℃, adding the solution B into the solution A under nitrogen atmosphere, stirring for 16 hours, filtering, centrifuging the residue for 10 minutes at 8500rpm after acid washing, alkali washing, brine washing and water washing, and drying the lower precipitate at 80 ℃ for 6 hours to obtain the modified carbon nanotube.
Example 4
A preparation method of a sound-insulating and shock-absorbing rubber composite material comprises the following steps:
55g of nitrile rubber, 15g of butyl rubber, 15g of ethylene propylene diene monomer, 5g of carbon black, 0.75g of N- (1, 3-dimethyl, butyl) -N-phenyl p-phenylenediamine, 0.75g of N, N-di-N-butyl dithiocarbamic acid nickel, 0.3g of 2, 4-trimethyl-1, 2-dihydroquinoline polymer, 0.5g of ethylene-propylene-diene thiourea and 0.1g of alkylated triethylenetetramine thiuram disulfide are mixed and banburying is carried out at 110 ℃, the rotating speed is 75rpm,60min, the mixture is mixed and banburying is carried out with 3g of modified carbon nano tube, 4.5g of sulfur, 5g of zinc oxide and 3g of stearic acid after 8 times of thin pass, and then extrusion is carried out, and vulcanization is carried out for 30min under 15MPa at 150 ℃, thus obtaining the sound insulation and shock absorption rubber composite material.
The preparation method of the modified carbon nano tube comprises the following steps:
s1, adding 3g of carboxylated carbon nano tubes and 7.5g of 3- (4-aminophenyl) -1, 2-propanediol into 500mL of N, N-dimethylformamide, adding 0.6g of 4-dimethylaminopyridine, and uniformly dispersing to obtain a solution A;
s2, adding 6g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride into 60mL of N, N-dimethylformamide, stirring uniformly to obtain a solution B, cooling the solution A to 0 ℃, adding the solution B into the solution A under nitrogen atmosphere, stirring for 16 hours, filtering, centrifuging the residue for 10 minutes at 8500rpm after acid washing, alkali washing, brine washing and water washing, and drying the lower precipitate at 80 ℃ for 6 hours to obtain the modified carbon nanotube.
Example 5
A preparation method of a sound-insulating and shock-absorbing rubber composite material comprises the following steps:
55g of nitrile rubber, 15g of butyl rubber, 15g of ethylene propylene diene monomer, 5g of carbon black, 0.75g of N- (1, 3-dimethyl, butyl) -N-phenyl p-phenylenediamine, 0.75g of N, N-di-N-butyl dithiocarbamic acid nickel, 0.3g of 2, 4-trimethyl-1, 2-dihydroquinoline polymer, 0.75g of ethylene-propylene-diene thiourea and 0.25g of alkylated triethylenetetramine thiuram disulfide are mixed and banburying is carried out at 110 ℃, the rotating speed is 75rpm,60min, the mixture is mixed and banburying is carried out with 5g of modified carbon nano tube, 4.5g of sulfur, 5g of zinc oxide and 3g of stearic acid after 8 times of thin pass, and then extrusion is carried out, and vulcanization is carried out for 30min under 15MPa at 150 ℃, thus obtaining the sound insulation and shock absorption rubber composite material.
The preparation method of the modified carbon nano tube comprises the following steps:
s1, adding 3g of carboxylated carbon nano tubes and 7.5g of 3- (4-aminophenyl) -1, 2-propanediol into 500mL of N, N-dimethylformamide, adding 0.6g of 4-dimethylaminopyridine, and uniformly dispersing to obtain a solution A;
s2, adding 6g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride into 60mL of N, N-dimethylformamide, stirring uniformly to obtain a solution B, cooling the solution A to 0 ℃, adding the solution B into the solution A under nitrogen atmosphere, stirring for 16 hours, filtering, centrifuging the residue for 10 minutes at 8500rpm after acid washing, alkali washing, brine washing and water washing, and drying the lower precipitate at 80 ℃ for 6 hours to obtain the modified carbon nanotube.
Test example 1
The rubber composite materials prepared in the comparative examples and the examples are subjected to mechanical property test, and the prepared samples are subjected to the same mechanical test after being treated for 2 days at 100 ℃ so as to obtain the heat aging resistance of the standard materials. Wherein the tensile strength is tested with reference to GB/T528-2009 determination of tensile stress strain properties of vulcanized rubber or thermoplastic rubber. Elongation at break was tested with reference to GB/T528-2009 determination of tensile stress Strain Properties of vulcanized rubber or thermoplastic rubber. Compression set is tested with reference to GB/T7759.1-2015 section 1 determination of compression set of vulcanized rubber or thermoplastic rubber at normal and high temperatures, specific test conditions being 70℃for 24h.
TABLE 1 mechanical Properties of rubber composite and results of thermal aging resistance test
As can be seen from a comparison of comparative example 1 and example 1, the modification of the carbon nanotubes is more pronounced than carboxylated carbon nanotubes for rubber composites, and because the carbon nanotubes themselves are very agglomerated, it can result in difficult sliding and riveting of the surrounding polymer chains, which reduces internal friction and energy dissipation during deformation of the composite, thereby reducing the damping properties of the composite. While the modification in example 1 results in groups on the surface of the carbon nanotubes capable of binding to
Nitrile groups in the nitrile rubber form hydrogen bonds, so that the slippage of polymer chains is limited, the interaction between carbon nanotubes is weakened, the agglomeration is prevented, pi-pi interaction can be formed by benzene rings of the nitrile rubber, and the accumulation inside the carbon nanotubes can be prevented. This is verified by the improvement of mechanical properties, wherein the improvement of tensile strength is caused by the good dispersion of the modified carbon nanotubes and the strong interfacial interaction between the modified carbon nanotubes and the matrix, the uniform dispersion of the filler can reduce the defects in the composite material, and the strong interfacial interaction between the modified filler and the matrix can limit the sliding of the rubber chain, and the carbon nanotubes themselves have high strength, so that the improvement of mechanical properties can be brought by adding the modified carbon nanotubes into the material.
Meanwhile, the rubber composite material in example 1 still maintains good mechanical properties after heat treatment due to the high thermal conductivity of the carbon nanotubes, which also proves that the addition of the modified carbon nanotubes can increase the damping temperature range of the material, resulting in an increase in thermal aging resistance. The modified carbon nanotubes of example 2 were non-covalently modified with polydopamine, which is relatively weak and therefore not as good as in example 1. In example 3, the amount of carbon black added was larger than that in example 1, and carbon black as a high structural material influences the structure of the crosslinked network in the material when the amount of carbon black added was large. The addition amount of the accelerator in example 4 was smaller than that in example 1, resulting in slower vulcanization speed, longer vulcanization time, and smaller hardness of the material, so that the elongation at break was larger, but on the other hand, the tensile strength was decreased. However, in example 5, when the amount of the modified carbon nanotubes is increased, agglomeration still occurs in the material, which not only damages the uniform dispersion of the carbon nanotubes, but also disables the high specific surface area effect thereof, thereby damaging the interfacial interaction between the filler and the matrix, and thus causing the performance to be degraded.
Test example 2
Damping performance and fatigue resistance tests are carried out on the rubber composite materials prepared in the comparative examples and the examples, and damping performance test conditions are as follows: the frequency is 1Hz, the temperature is 25 ℃, and the strain range is 50-100%; the fatigue life was measured with reference to GB/T1687-2016 "measurement of temperature rise and fatigue resistance of vulcanized rubber in flexural test".
Table 2 damping properties and fatigue resistance test results table of sound-insulating and shock-absorbing rubber
Experimental protocol Loss factor tan delta Fatigue life/ten thousand times
Comparative example 1 0.34 52.5
Example 1 0.395 58.6
Example 2 0.312 48.7
Example 3 0.351 54.2
Example 4 0.346 52.0
Example 5 0.282 40.2
The filler is the most obvious factor influencing the damping performance of rubber except the rubber material, and has close relation with the damping coefficient and modulus of vulcanized rubber. When the molecular chain of rubber moves, internal friction is generated between the rubber chain segment and the filler and between the filler particles, and the interaction between the rubber and the filler increases the loss factor of vulcanized rubber. The smaller the size of the filler particles, the larger the specific surface area, and the larger the internal friction between the fillers and the rubber increases due to the increase of the contact area, and the larger the mechanical loss is generated when the molecular chain moves, so the loss factor is larger. The better the activity of the filler, the greater the interaction with the rubber molecules, with a consequent increase in the stiffness and damping properties of the vulcanizate. Therefore, when the carbon nanotubes are modified, the damping performance is not reduced but improved, because the modified carbon nanotubes can form stronger interface interaction with the material, the defects in the composite material can be reduced by uniformly dispersing the carbon nanotubes, and the slippage of the rubber chain can be limited by the strong interface interaction between the modified filler and the matrix, so that the loss factor is increased. The improvement of damping performance correspondingly prolongs the fatigue life of the rubber composite material, so that the material is suitable for being used as a sound insulation and shock absorption material in the field of automobiles.

Claims (2)

1. The sound-insulating and shock-absorbing rubber composite material is characterized by comprising the following raw materials: 55g of nitrile rubber, 15g of butyl rubber, 15g of ethylene propylene diene monomer, 5g of carbon black, 0.75g of N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine, 0.75g of nickel N, N-di-N-butyldithiocarbamic acid, 0.3g of 2, 4-trimethyl-1, 2-dihydroquinoline polymer, 0.75g of ethylene-propylene-diene thiourea, 0.25g of alkylated triethylenetetramine thiuram disulfide, 3g of modified carbon nano tube, 4.5g of sulfur, 5g of zinc oxide and 3g of stearic acid;
the preparation method of the modified carbon nano tube comprises the following steps:
s1, adding 3g of carboxylated carbon nano tubes and 7.5g of 3- (4-aminophenyl) -1, 2-propanediol into 500mL of N, N-dimethylformamide, adding 0.6g of 4-dimethylaminopyridine, and uniformly dispersing to obtain a solution A;
s2, adding 6g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride into 60mL of N, N-dimethylformamide, stirring uniformly to obtain a solution B, cooling the solution A to 0 ℃, adding the solution B into the solution A under nitrogen atmosphere, stirring for 16 hours, filtering, centrifuging the residue for 10 minutes at 8500rpm after acid washing, alkali washing, brine washing and water washing, and drying the lower precipitate at 80 ℃ for 6 hours to obtain the modified carbon nanotube.
2. The sound and shock absorbing rubber composite of claim 1, wherein: the method comprises the following steps:
mixing nitrile rubber, butyl rubber, ethylene propylene diene monomer, carbon black, N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine, N-di-N-butyl dithiocarbamic acid nickel, 2, 4-trimethyl-1, 2-dihydroquinoline polymer, ethylene-propylene-diene thiourea and alkylated triethylenetetramine thiuram disulfide, banburying at 110 ℃, mixing and banburying with modified carbon nano tube, sulfur, zinc oxide and stearic acid after 60min, extruding after 8 times of thinning, and vulcanizing at 150 ℃ and 15MPa for 30min to obtain the modified carbon nano tube.
CN202311317105.5A 2023-10-12 2023-10-12 Sound-insulating and shock-absorbing rubber composite material and preparation method thereof Active CN117050402B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311317105.5A CN117050402B (en) 2023-10-12 2023-10-12 Sound-insulating and shock-absorbing rubber composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311317105.5A CN117050402B (en) 2023-10-12 2023-10-12 Sound-insulating and shock-absorbing rubber composite material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN117050402A CN117050402A (en) 2023-11-14
CN117050402B true CN117050402B (en) 2023-12-29

Family

ID=88654004

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311317105.5A Active CN117050402B (en) 2023-10-12 2023-10-12 Sound-insulating and shock-absorbing rubber composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN117050402B (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107200883A (en) * 2017-06-28 2017-09-26 常州市瑞泰物资有限公司 A kind of damping rubber material
CN109777007A (en) * 2019-02-22 2019-05-21 华研(佛山)纳米材料有限公司 A kind of carbon nanotube polyvinyl chloride composite materials and preparation method thereof
CN109851868A (en) * 2019-02-22 2019-06-07 华研(佛山)纳米材料有限公司 A kind of tire material of carbon nanotubes and preparation method thereof
CN113185906A (en) * 2021-05-18 2021-07-30 扬州工业职业技术学院 Water-based anticorrosive paint
CN114395297A (en) * 2022-03-05 2022-04-26 浙江柏德密封科技有限公司 Sealing gasket coated with fluororubber and production process thereof
CN115240927A (en) * 2022-07-27 2022-10-25 安徽长鹿特种电缆有限公司 Preparation method of roller cable
CN115873321A (en) * 2021-09-28 2023-03-31 江苏金风科技有限公司 Damping material and preparation method and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107200883A (en) * 2017-06-28 2017-09-26 常州市瑞泰物资有限公司 A kind of damping rubber material
CN109777007A (en) * 2019-02-22 2019-05-21 华研(佛山)纳米材料有限公司 A kind of carbon nanotube polyvinyl chloride composite materials and preparation method thereof
CN109851868A (en) * 2019-02-22 2019-06-07 华研(佛山)纳米材料有限公司 A kind of tire material of carbon nanotubes and preparation method thereof
CN113185906A (en) * 2021-05-18 2021-07-30 扬州工业职业技术学院 Water-based anticorrosive paint
CN115873321A (en) * 2021-09-28 2023-03-31 江苏金风科技有限公司 Damping material and preparation method and application thereof
CN114395297A (en) * 2022-03-05 2022-04-26 浙江柏德密封科技有限公司 Sealing gasket coated with fluororubber and production process thereof
CN115240927A (en) * 2022-07-27 2022-10-25 安徽长鹿特种电缆有限公司 Preparation method of roller cable

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Preparation and Properties of Rubber Blends for High-Damping Isolation Bearings;Tuo Lei等;《Polymers》;第11卷;1-18 *

Also Published As

Publication number Publication date
CN117050402A (en) 2023-11-14

Similar Documents

Publication Publication Date Title
US9422413B1 (en) Elastomer formulations comprising discrete carbon nanotube fibers
JP6082591B2 (en) Rubber composition
CN106893155B (en) A kind of vibration damping rubber and its application
US20130065991A1 (en) Vibration-proof rubber composition for automobile
TWI571489B (en) Improved natural rubber compositions
EP2845869B1 (en) Modified natural rubber, method for producing same, rubber composition, and tire
EP1161494B1 (en) Elastomeric compositions for damping
Kazemi et al. Hybrid nanocellulose/carbon nanotube/natural rubber nanocomposites with a continuous three‐dimensional conductive network
DE602004000963T2 (en) Rubber composition and pneumatic tire made therewith
EP2650325A1 (en) Polymer mixture, rubber mixture comprising the polymer mixture and process for preparing the rubber mixture
CN117050402B (en) Sound-insulating and shock-absorbing rubber composite material and preparation method thereof
Gao et al. Fabricated coordinate and ionic bonds in chemically cross‐linked ethylene acrylic elastomer for high‐performing elastomers
JP2006131819A (en) Rubber composition for vibration proofing rubber, and vibration proofing rubber
KR101846707B1 (en) Anti vibration rubber composition improved vibration isolation and Anti vibration rubber
JP6977259B2 (en) Pneumatic tires
JP2006143860A (en) Rubber vibration insulator
JPH07268148A (en) Rubber composition for heat-resistant rubber vibration insulator
JP2006193617A (en) Vibration-proof rubber composition and vibration-proof rubber
CN114891281B (en) Simplified method for simultaneously optimizing mechanical property, low heat generation and wear resistance of graphene modified natural rubber vulcanized rubber
Du et al. Enhanced rheological properties of carbon nanotubes reinforced natural rubber/butadiene rubber nanocomposites
KR100590976B1 (en) A rubber composition for engine mount with improved heat and age resistance
JP7296414B2 (en) Anti-vibration rubber composition and anti-vibration rubber
KR101496243B1 (en) Rubber composition for tire hump strip and tire manufactured by using the same
JP2013124346A (en) Rubber composition
EP4122984A1 (en) Rubber compositions

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant