CN113150401A - Low-temperature-resistant and aging-resistant rubber material and preparation method thereof - Google Patents
Low-temperature-resistant and aging-resistant rubber material and preparation method thereof Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 241
- 239000005060 rubber Substances 0.000 title claims abstract description 241
- 230000032683 aging Effects 0.000 title claims abstract description 58
- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 43
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 43
- 229920001194 natural rubber Polymers 0.000 claims abstract description 43
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims abstract description 42
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- JBAUPCNQUQGXJT-UHFFFAOYSA-N 1-ethenyl-4-methylbenzene;2-methylprop-1-ene Chemical group CC(C)=C.CC1=CC=C(C=C)C=C1 JBAUPCNQUQGXJT-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 35
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 32
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000004073 vulcanization Methods 0.000 claims abstract description 28
- 239000003607 modifier Substances 0.000 claims abstract description 27
- 239000004014 plasticizer Substances 0.000 claims abstract description 24
- 239000013543 active substance Substances 0.000 claims abstract description 20
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 19
- 229920001084 poly(chloroprene) Polymers 0.000 claims abstract description 13
- 230000004048 modification Effects 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 9
- 230000031709 bromination Effects 0.000 claims abstract description 7
- 238000005893 bromination reaction Methods 0.000 claims abstract description 7
- 229920005557 bromobutyl Polymers 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 98
- 150000001875 compounds Chemical class 0.000 claims description 52
- 238000007599 discharging Methods 0.000 claims description 34
- 239000006229 carbon black Substances 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 14
- JNRBECNFJNRQAS-UHFFFAOYSA-N C(C(C)Br)Br.C=C Chemical compound C(C(C)Br)Br.C=C JNRBECNFJNRQAS-UHFFFAOYSA-N 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- MBDNRNMVTZADMQ-UHFFFAOYSA-N sulfolene Chemical compound O=S1(=O)CC=CC1 MBDNRNMVTZADMQ-UHFFFAOYSA-N 0.000 claims description 7
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 claims description 6
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005662 Paraffin oil Substances 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 21
- 238000000034 method Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 13
- 239000012190 activator Substances 0.000 description 11
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- 239000000758 substrate Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 101100478969 Oryza sativa subsp. japonica SUS2 gene Proteins 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 101100004663 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) BRR2 gene Proteins 0.000 description 2
- 101100504519 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) GLE1 gene Proteins 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000007405 data analysis Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 238000003878 thermal aging Methods 0.000 description 2
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- STSDHUBQQWBRBH-UHFFFAOYSA-N n-cyclohexyl-1,3-benzothiazole-2-sulfonamide Chemical compound N=1C2=CC=CC=C2SC=1S(=O)(=O)NC1CCCCC1 STSDHUBQQWBRBH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
- B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/005—Methods for mixing in batches
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/22—Component parts, details or accessories; Auxiliary operations
- B29B7/28—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control
- B29B7/286—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control measuring properties of the mixture, e.g. temperature, density
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/283—Halogenated homo- or copolymers of iso-olefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/06—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
- B29B7/10—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary
- B29B7/18—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft
- B29B7/183—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft having a casing closely surrounding the rotors, e.g. of Banbury type
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a low-temperature-resistant and aging-resistant rubber material and a preparation method thereof. The rubber material comprises the following components in parts by weight: 100 parts of raw rubber, 7 parts of an active agent, 4 parts of an anti-aging agent, 1-3 parts of a modifier, 52 parts of a reinforcing agent, 8 parts of a processing aid, 6 parts of a plasticizer and 4.5 parts of a vulcanization accelerator; the raw rubber comprises rubber A, rubber B and rubber C, wherein the rubber A is natural rubber, the rubber B is brominated isobutylene p-methylstyrene rubber or chloroprene rubber or brominated butyl rubber, the rubber C is brominated ethylene propylene rubber, and the brominated ethylene propylene rubber is obtained by bromination modification of ethylene propylene diene monomer. The rubber material disclosed by the invention is high in low-temperature resistance and aging resistance, and solves the technical problems that an air spring made of the rubber material in the prior art cannot meet the operation requirement in a high-cold environment at minus 50 ℃ and is short in service life.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a low-temperature-resistant and aging-resistant rubber material and a preparation method thereof.
Background
The air spring system has the following disadvantages that the air spring system is prepared from an important functional element air bag made of rubber materials and is influenced by material performance:
firstly, when the rubber is used in a low-temperature environment (-50 ℃) in a severe cold area, the reliability of a product is poor, and when the rubber is used as a high polymer material, brittle failure is easy to generate when the brittle temperature is reached;
and secondly, the rubber material is used as a chemical material, chemical aging is always generated in the application process, aging, cracking and damage are formed, the final product is invalid, and the rubber material needs to be periodically overhauled and replaced.
In order to reduce the aging of the rubber air bag and improve the fatigue resistance, chloroprene rubber is adopted as a main rubber seed of an air bag rubber material in the prior art, the chloroprene rubber has excellent aging resistance, and the aging resistance of the air spring air bag can be effectively improved, so that the service life of the air spring air bag can reach 6-8 years. However, the chloroprene rubber has poor low-temperature performance, and an air bag product made of the chloroprene rubber loses elasticity at about-40 ℃, so that brittle failure or air tightness reduction of a rubber material is easily caused, the reliability of the air spring is reduced, and the normal operation of a train in a high and cold environment at-50 ℃ is influenced. At present, no effective solution is provided for the problems that the product made of rubber material has poor aging resistance and can not meet the use requirement in a high and cold environment at minus 50 ℃.
Disclosure of Invention
The invention provides a low-temperature-resistant and aging-resistant rubber material and a preparation method thereof. The rubber material has good low-temperature resistance and aging resistance, the mechanical property of the air spring prepared by the rubber material meets the standard requirement, and meanwhile, the air spring can still be normally used at the temperature of 50 ℃ below zero, and the service life is longer.
In order to achieve the above purpose, one aspect of the present invention provides a low temperature resistant and aging resistant rubber compound, which comprises the following components in parts by weight: 100 parts of raw rubber, 7 parts of an active agent, 4 parts of an anti-aging agent, 1-3 parts of a modifier, 52 parts of a reinforcing agent, 8 parts of a processing aid, 6 parts of a plasticizer and 4.5 parts of a vulcanization accelerator; the raw rubber comprises rubber A, rubber B and rubber C, wherein the rubber A is natural rubber, the rubber B is brominated isobutylene p-methylstyrene rubber or chloroprene rubber or brominated butyl rubber, the rubber C is brominated ethylene propylene rubber, and the brominated ethylene propylene rubber is obtained by bromination modification of ethylene propylene diene monomer.
Preferably, the rubber B is brominated isobutylene p-methylstyrene rubber, and the raw rubber comprises the following specific components in parts by mass: 35-40 parts of natural rubber, 35-40 parts of brominated isobutylene p-methylstyrene rubber and 20-30 parts of brominated ethylene propylene rubber.
Preferably, the natural rubber is smoked sheet rubber or SMR 5L;
0.75% of benzyl bromide of the brominated isobutylene p-methylstyrene;
the ethylene content of the ethylene-propylene-diene monomer rubber is 53-67%, and the content of a third monomer of the ethylene-propylene-diene monomer rubber is 9-11%.
Preferably, the natural rubber is tobacco sheet rubber RSS 1; the ethylene-propylene-diene monomer rubber has a vinyl content of 54 percent, the third monomer of the ethylene-propylene-diene monomer rubber is ENB, and the ENB content is 10.5 percent.
Preferably, the active agent comprises the following specific components in parts by mass: 5 parts of zinc oxide and 2 parts of stearic acid.
Preferably, the anti-aging agent comprises the following specific components in parts by mass: 40201 parts, RD 1 part, and paraffin wax 2 parts.
Preferably, the reinforcing agent comprises the following specific components in parts by mass: 34 parts of carbon black and 18 parts of white carbon black.
Preferably, the white carbon black has a specific surface area of more than 150m2White carbon black in a ratio of/g.
Preferably, the modifier comprises a silane coupling agent, and the mass of the silane coupling agent is 10% of the mass of the white carbon black.
Preferably, the processing aid comprises a Koresin tackifying resin and an aromatic hydrocarbon resin.
Preferably, the plasticizer is paraffin oil.
Preferably, the vulcanization accelerator includes sulfur, alkyl dithiophosphate, dicumyl peroxide, N-cyclohexyl-2-benzothiazolesulfenamide.
Another aspect of the present invention provides a method for preparing a rubber compound resistant to low temperature aging according to any one of the above technical solutions, comprising the following steps:
s1, preparing brominated ethylene propylene rubber, mixing 1 g and 3 g of butadiene sulfone and a brominating agent N-1, 3-brominated-dimethylhexanoyl amide, dissolving in 50ml of ethyl acetate, and stirring until the mixture is completely dissolved to prepare liquid for later use;
s2, adding 30kg of ethylene propylene diene monomer into an internal mixer, mixing and heating to 40-50 ℃, adding the liquid to be used in the step 1, continuously mixing to 70 ℃, keeping for 1-2 min, and discharging to obtain ethylene propylene bromide rubber;
s3, putting the natural rubber, the rubber B and the ethylene propylene bromide rubber into an internal mixer, and mixing for 30-45S;
s4, adding the modifier and the reinforcing agent into an internal mixer, and mixing for 30-40S;
s5, putting the active agent and the anti-aging agent into an internal mixer together, and mixing for 45-60S;
s6, putting the plasticizer into an internal mixer, mixing to 130 ℃, and continuously mixing for 80-90S at the temperature of 130-135 ℃ by using an equipment temperature control module;
s7, discharging the rubber to a sheet discharging machine, performing air cooling to obtain master batch, and standing for more than 2 hours;
s8, putting the cooled and parked master batch into an internal mixer, and mixing for 30-40S;
and S9, adding a vulcanization accelerator into the internal mixer, mixing for 30-40S, lifting and lifting the internal mixer to a top bolt for 1 time, discharging the rubber when the mixture is mixed to 100 ℃, and cooling to obtain the low-temperature-resistant and aging-resistant rubber material.
Preferably, in the steps S1 to S5, the rotating speed of the internal mixer is 35 to 45 r/min.
Preferably, in the steps S6 to S7, the rotating speed of the internal mixer is 15 to 20 r/min.
The invention further provides an air spring which comprises an air bag, wherein the air bag is prepared by vulcanizing the low-temperature-resistant and aging-resistant rubber compound in any one technical scheme.
Compared with the prior art, the invention has the advantages that: the invention provides a low-temperature-resistant and aging-resistant rubber material, a preparation method thereof and an air spring. The air spring made of the rubber material can meet the requirements of comfort and safety of operation in high and cold low-temperature environments at minus 50 ℃. Specifically, the method comprises the following steps:
1. the rubber material provided by the invention preferably takes raw rubber consisting of natural rubber, brominated isobutylene p-methylstyrene rubber and brominated ethylene-propylene rubber as a main material, wherein the brominated ethylene-propylene rubber is prepared by bromination modification treatment of ethylene-propylene-diene monomer rubber, so that the mixing uniformity among different rubbers can be improved; by utilizing the blending effect of the brominated ethylene-propylene rubber, the excellent low-temperature performance of natural rubber and the better aging resistance of brominated isobutylene p-methylstyrene rubber are kept, and the reasonable mass parts of reinforcing agents comprising white carbon black and carbon black, processing aids, anti-aging agents and other auxiliary agents are added, so that the mechanical property, the low-temperature resistance and the aging resistance of rubber materials are further improved.
2. The processing aid for preparing the rubber material comprises Koresin tackifying resin and aromatic hydrocarbon resin, enhances the self-adhesiveness of the rubber material, and is convenient for improving the stability of the rubber material in the molding process of later-stage manufactured products.
3. The preparation method provided by the invention is simple and is convenient for large-scale industrial production.
4. The preparation method provided by the invention comprises the steps of preparing the brominated ethylene propylene rubber, adding the prepared brominated ethylene propylene rubber, the natural rubber and the brominated isobutylene p-methylstyrene rubber into an internal mixer for mixing, adding the auxiliary agents in a certain sequence and mixing. When the auxiliary agent is added and mixed, the modifier and the reinforcing agent are added together, and then the activator and the anti-aging agent are added together. The modifier and the reinforcing agent are fully contacted with the rubber matrix, the mixing uniformity of the three rubbers is improved by adding the modifier, the reinforcing effect of the reinforcing agent is enhanced, and meanwhile, the combination difference of different rubber matrixes to the reinforcing agent is reduced, so that the reinforcing agent is more uniformly dispersed in different rubber matrixes; after the reinforcing agent is uniformly dispersed, the active agent and the anti-aging agent are added, so that the phenomenon that the reinforcing agent adsorbs the active agent and the anti-aging agent to influence the activation effect and the anti-aging effect is avoided, and the mechanical performance of the rubber material is further improved.
5. The rubber material provided by the invention can be used for preparing an air spring air bag, an air spring with the air bag can meet the use requirement at the temperature of-50 ℃, the service life is long, various performances meet the requirements of the standard TB/T2841-2019, and the technical problems that the air spring in the prior art cannot be used in a high and cold environment and the service life is short are solved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is described and illustrated below with reference to the embodiments. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments provided in the present application without any inventive step are within the scope of protection of the present application.
It is obvious that the following describes only some examples or embodiments of the present application, and that it is also possible for a person skilled in the art to apply the present application to other similar situations without inventive effort. Moreover, it should be appreciated that in the development of any such actual implementation, as in any engineering or design project, numerous implementation-specific decisions must be made to achieve the developers' specific goals, such as compliance with system-related and business-related constraints, which may vary from one implementation to another.
Reference in the specification to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the specification. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of ordinary skill in the art will explicitly and implicitly appreciate that the embodiments described herein may be combined with other embodiments without conflict.
Unless otherwise defined, technical or scientific terms referred to herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this application belongs. Reference to "a," "an," "the," and similar words throughout this application are not to be construed as limiting in number, and may refer to the singular or the plural. The present application is directed to the use of the terms "including," "comprising," "having," and any variations thereof, which are intended to cover non-exclusive inclusions; the term "plurality" as referred to herein means two or more. "and/or" describes an association relationship of associated objects, meaning that three relationships may exist, for example, "a and/or B" may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the front and back associated objects are in an "or" relationship. Reference herein to the terms "first," "second," "third," and the like, are merely to distinguish similar objects and do not denote a particular ordering for the objects.
The embodiment of the invention provides a low-temperature-resistant and aging-resistant rubber compound which comprises the following components in parts by weight: 100 parts of raw rubber, 7 parts of an active agent, 4 parts of an anti-aging agent, 1-3 parts of a modifier, 52 parts of a reinforcing agent, 8 parts of a processing aid, 6 parts of a plasticizer and 4.5 parts of a vulcanization accelerator; the raw rubber comprises rubber A, rubber B and rubber C, the mass ratio of the rubber A to the rubber B to the rubber C is (35-40): 20-30), wherein the rubber A is natural rubber, the rubber B is brominated isobutylene p-methylstyrene rubber or chloroprene rubber or brominated butyl rubber, the rubber C is brominated ethylene propylene rubber, and the brominated ethylene propylene rubber is obtained by bromination modification of ethylene propylene diene monomer.
The rubber compound provided by the embodiment is prepared by mixing raw rubber including rubber A, rubber B and rubber C as a base material, wherein the rubber A is natural rubber, the rubber B is one of brominated isobutylene p-methylstyrene rubber or chloroprene rubber or brominated butyl rubber, the rubber C is brominated ethylene propylene rubber, and a modifier, a reinforcing agent, an active agent, an anti-aging agent, a processing aid, a plasticizer and a vulcanization accelerator are used as auxiliary materials, and the rubber compound has the characteristics of excellent low temperature resistance, aging resistance and the like.
In a preferred embodiment, the rubber B is brominated isobutylene p-methylstyrene rubber, and the raw rubber comprises the following specific components in parts by mass: 35-40 parts of natural rubber, 35-40 parts of brominated isobutylene p-methylstyrene rubber and 20-30 parts of brominated ethylene propylene rubber. In the preferred embodiment, the brominated ethylene propylene rubber is obtained by self-making modification of ethylene propylene diene monomer, and after bromination modification, the mixing uniformity of different rubbers can be improved, and the interface bonding capability of different rubbers can be improved. Specifically, the natural rubber has excellent low-temperature performance and processability, but the aging resistance is poor, the brominated isobutylene p-methylstyrene rubber has better aging resistance and excellent low-temperature resistance, but the processability is poor, and the combination of the brominated isobutylene p-methylstyrene rubber and the brominated isobutylene p-methylstyrene rubber can ensure that the blended rubber has better low-temperature resistance and aging resistance at the same time, but the compatibility of the brominated isobutylene p-methylstyrene rubber and the natural rubber is poor. The brominated ethylene-propylene rubber can be used as a compatilizer, has the function of blending modification and improves the mixing uniformity among different rubbers.
In a preferred embodiment, the natural rubber is smoked sheet rubber or SMR 5L;
0.75% of benzyl bromide of the brominated isobutylene p-methylstyrene;
the ethylene content of the ethylene-propylene-diene monomer rubber is 53-67%, and the content of a third monomer of the ethylene-propylene-diene monomer rubber is 9-11%. The ethylene propylene diene monomer with high ethylene content has higher mechanical strength than ethylene propylene diene monomer with low ethylene content (below 50%), is favorable for improving the mechanical property of the whole rubber material, and can improve the tensile strength by 10-15%.
In a preferred embodiment, the natural rubber is tabstock RSS 1; the ethylene-propylene-diene monomer rubber has a vinyl content of 54 percent, the third monomer of the ethylene-propylene-diene monomer rubber is ENB, and the ENB content is 10.5 percent. The ethylene propylene diene monomer with high ENB content has lower chemical reaction activity and higher ENB content, is beneficial to realizing co-vulcanization with other rubber in rubber compound, and improves the mechanical property and tensile strength of the whole rubber compound by 20-25%.
In a preferred embodiment, the active agent comprises the following specific components in parts by mass: 5 parts of zinc oxide and 2 parts of stearic acid.
In a preferred embodiment, the anti-aging agent comprises the following specific components in parts by mass: 40201 parts, RD 1 part, and paraffin wax 2 parts.
In a preferred embodiment, the reinforcing agent comprises the following specific components in parts by mass: 34 parts of carbon black and 18 parts of white carbon black; the white carbon black is preferably white carbon black with specific surface area more than 150m2White carbon black in a ratio of/g. Specifically, the white carbon black has the synergistic effects of reinforcement and wear resistance, and can improve the mechanical property of the sizing material. Besides, the mixing proportion of the white carbon black needs to be controlled, the selection of the specific surface area and the dispersion characteristic of the mark is also critical, and the specific surface area needs to be controlled to be 150m2More than g and has high dispersion property. To obtain good dispersing effect and mechanical properties.
In a preferred embodiment, the modifier comprises a silane coupling agent, and the mass of the silane coupling agent is 10% of the mass of the white carbon black. The silane coupling agent is beneficial to the dispersion of the white carbon black in the rubber matrix, and chemical bonding is formed between the white carbon black and the rubber matrix, so that the molecular bonding of the white carbon black and the rubber matrix is enhanced, and through tests, when the dosage of the silane coupling agent is 10% of the mass of the white carbon black, the bonding force of the white carbon black and the rubber matrix is the largest, the white carbon black has the best reinforcing effect, the dosage of the silane coupling agent exceeds 10%, and the reinforcing effect is not increased any more.
In a preferred embodiment, the processing aids are Koresin tackifying resins and aromatic hydrocarbon resins. The addition of the Koresin tackifying resin hardly influences the mechanical properties of the rubber compound, but can increase the self-viscosity of the rubber compound and improve the stability of the rubber compound in the subsequent air bag forming process. The addition of the aromatic hydrocarbon resin can reduce the interfacial tension of the natural rubber and the ethylene propylene diene monomer rubber and promote the natural rubber and the ethylene propylene diene monomer rubber to achieve better compatibility.
In a preferred embodiment, the plasticizer is a paraffin oil.
In a preferred embodiment, the vulcanization accelerator is sulfur, alkyl dithiophosphate, dicumyl peroxide, N-cyclohexyl-2-benzothiazyl sulfenamide. The alkyl dithiophosphate and the dicumyl peroxide can simultaneously vulcanize natural rubber, ethylene propylene rubber and brominated isobutylene p-methylstyrene rubber, the solubility distribution parameters of the alkyl dithiophosphate and the dicumyl peroxide are nearly consistent, synchronous vulcanization of the alkyl dithiophosphate and the ethylene propylene rubber and synchronous vulcanization of the brominated isobutylene p-methylstyrene rubber are convenient to realize, the mechanical property of rubber materials is improved, and the problem of vulcanization blooming caused by solubility difference is avoided.
Another aspect of the present invention provides a method for preparing a rubber compound resistant to low temperature aging according to any one of the above technical solutions, comprising the following steps:
s1, preparing brominated ethylene propylene rubber, mixing 1 g and 3 g of butadiene sulfone and a brominating agent N-1, 3-brominated-dimethylhexanoyl amide, dissolving in 50ml of ethyl acetate, and stirring until the mixture is completely dissolved to prepare liquid for later use;
s2, adding 30kg of ethylene propylene diene monomer into an internal mixer, mixing and heating to 40-50 ℃, adding the liquid to be used in the step 1, continuously mixing to 70 ℃, keeping for 1-2 min, and discharging to obtain ethylene propylene bromide rubber;
s3, putting the natural rubber, the rubber B and the ethylene propylene bromide rubber into an internal mixer, and mixing for 30-45S;
s4, adding the modifier and the reinforcing agent into an internal mixer, and mixing for 30-40S;
s5, putting the active agent and the anti-aging agent into an internal mixer together, and mixing for 45-60S;
s6, putting the plasticizer into an internal mixer, mixing to 130 ℃, and continuously mixing for 80-90S at the temperature of 130-135 ℃ by using an equipment temperature control module;
s7, discharging the rubber to a sheet discharging machine, performing air cooling to obtain master batch, and standing for more than 2 hours;
s8, putting the cooled and parked master batch into an internal mixer, and mixing for 30-40S;
and S9, adding a vulcanization accelerator into the internal mixer, mixing for 30-40S, lifting and lifting the internal mixer to a top bolt for 1 time, discharging the rubber when the mixture is mixed to 100 ℃, and cooling to obtain the low-temperature-resistant and aging-resistant rubber material.
In a preferred embodiment, in the steps S1 to S5, the rotation speed of the internal mixer is 35 to 45 r/min.
In a preferred embodiment, in the steps S6 to S7, the rotation speed of the internal mixer is 15 to 20 r/min.
This example provides a method of preparing a low temperature and aging resistant rubber compound as set forth in the preceding examples. Firstly, preparing brominated ethylene-propylene rubber, then putting the prepared brominated ethylene-propylene rubber, natural rubber and rubber B into an internal mixer for mixing according to parts by weight, preferably brominated isobutylene p-methylstyrene rubber, and then adding various auxiliary modifiers, reinforcing agents, activators, anti-aging agents, processing aids, plasticizers, vulcanization accelerators and the like into the internal mixer for mixing according to the step sequence and parts by weight. The brominated ethylene-propylene rubber in the preparation method is ethylene-propylene-diene monomer rubber, after bromination modification treatment, the self-adhesiveness and the chemical activity of the brominated ethylene-propylene-diene monomer rubber are improved, and other properties are unchanged, so that the mixing uniformity among different types of rubber can be improved. The preparation method prepares the rubber material with high low-temperature resistance and aging resistance through reasonable collocation and optimization of natural rubber, brominated isobutylene p-methylstyrene rubber, brominated ethylene-propylene rubber, tackifying resin, uniform resin and white carbon black.
The invention further provides an air spring which comprises an air bag, wherein the air bag is prepared by vulcanizing the low-temperature-resistant and aging-resistant rubber compound in any one technical scheme. The air spring can meet the use requirement at the temperature of 50 ℃ below zero, and all performances meet the requirements of the standard TB/T2841-2019.
In order to more clearly and specifically describe the low temperature and aging resistant rubber compound provided in the examples of the present invention, the preparation method and the application thereof, the following description will be made with reference to the specific examples and the comparative examples.
Example 1
The rubber compound comprises the following components in parts by mass:
35 parts of natural rubber, 35 parts of brominated isobutylene p-methylstyrene rubber, 30 parts of brominated ethylene propylene rubber, 7 parts of an activator, 4 parts of an anti-aging agent, 1 part of a modifier, 52 parts of a reinforcing agent, 8 parts of a processing aid, 6 parts of a plasticizer and 4.5 parts of a vulcanization accelerator.
The preparation method comprises the following specific steps:
manufacturing equipment and key process parameters: the meshing internal mixer with the nominal volume of more than 90L has the temperature of the temperature control unit set within the range of 30-40 ℃ and the top plug pressure of 0.5 MPa. The rotor speed of the internal mixer in the following steps 1-5 is 35-45 r/min, and the rotor speed of the internal mixer in the steps 6-7 is 15-20 r/min.
S1, preparing brominated ethylene propylene rubber, mixing 1 g and 3 g of butadiene sulfone and a brominating agent N-1, 3-brominated-dimethylhexanoyl amide, dissolving in 50ml of ethyl acetate, and stirring until the mixture is completely dissolved to prepare liquid for later use;
s2, adding 30kg of ethylene propylene diene monomer into an internal mixer, mixing and heating to 40-50 ℃, adding the liquid to be used in the step 1, continuously mixing to 70 ℃, keeping for 1-2 min, and discharging to obtain ethylene propylene bromide rubber;
s3, putting natural rubber, brominated isobutylene p-methylstyrene rubber and brominated ethylene propylene rubber into an internal mixer, and mixing for 30-45S;
s4, adding the modifier and the reinforcing agent into an internal mixer, and mixing for 30-40S;
s5, putting the active agent and the anti-aging agent into an internal mixer together, and mixing for 45-60S;
s6, putting the plasticizer into an internal mixer, mixing to 130 ℃, and continuously mixing for 80-90S at the temperature of 130-135 ℃ by using an equipment temperature control module;
s7, discharging the rubber to a sheet discharging machine, performing air cooling to obtain master batch, and standing for more than 2 hours;
s8, putting the cooled and parked master batch into an internal mixer, and mixing for 30-40S;
and S9, adding a vulcanization accelerator into the internal mixer, mixing for 30-40S, lifting and lifting the internal mixer to a top bolt for 1 time, discharging the rubber when the mixture is mixed to 100 ℃, and cooling to obtain the low-temperature-resistant and aging-resistant rubber material.
Among them, the natural rubber in example 1 is preferably smoked sheet rubber RSS1, and the ethylene-propylene-diene monomer rubber with the ethylene content of 53% and the third monomer content of 9% is preferably used for preparing ethylene-propylene-bromide rubber.
Example 2
The rubber compound comprises the following components in parts by mass:
40 parts of natural rubber, 40 parts of brominated isobutylene p-methylstyrene rubber, 20 parts of brominated ethylene propylene rubber, 7 parts of an activator, 4 parts of an anti-aging agent, 3 parts of a modifier, 52 parts of a reinforcing agent, 8 parts of a processing aid, 6 parts of a plasticizer and 4.5 parts of a vulcanization accelerator.
The preparation method comprises the following specific steps:
manufacturing equipment and key process parameters: the meshing internal mixer with the nominal volume of more than 90L has the temperature of the temperature control unit set within the range of 30-40 ℃ and the top plug pressure of 0.5 MPa. The rotor speed of the internal mixer in the following steps 1-5 is 35-45 r/min, and the rotor speed of the internal mixer in the steps 6-7 is 15-20 r/min.
S1, preparing brominated ethylene propylene rubber, mixing 1 g and 3 g of butadiene sulfone and a brominating agent N-1, 3-brominated-dimethylhexanoyl amide, dissolving in 50ml of ethyl acetate, and stirring until the mixture is completely dissolved to prepare liquid for later use;
s2, adding 30kg of ethylene propylene diene monomer into an internal mixer, mixing and heating to 40-50 ℃, adding the liquid to be used in the step 1, continuously mixing to 70 ℃, keeping for 1-2 min, and discharging to obtain ethylene propylene bromide rubber;
s3, putting natural rubber, brominated isobutylene p-methylstyrene rubber and brominated ethylene propylene rubber into an internal mixer, and mixing for 30-45S;
s4, adding the modifier and the reinforcing agent into an internal mixer, and mixing for 30-40S;
s5, putting the active agent and the anti-aging agent into an internal mixer together, and mixing for 45-60S;
s6, putting the plasticizer into an internal mixer, mixing to 130 ℃, and continuously mixing for 80-90S at the temperature of 130-135 ℃ by using an equipment temperature control module;
s7, discharging the rubber to a sheet discharging machine, performing air cooling to obtain master batch, and standing for more than 2 hours;
s8, putting the cooled and parked master batch into an internal mixer, and mixing for 30-40S;
and S9, adding a vulcanization accelerator into the internal mixer, mixing for 30-40S, lifting and lifting the internal mixer to a top bolt for 1 time, discharging the rubber when the mixture is mixed to 100 ℃, and cooling to obtain the low-temperature-resistant and aging-resistant rubber material.
Among them, in example 2, the natural rubber is preferably smoked sheet rubber RSS1, preferably 0.75% of benzyl bromide of brominated isobutylene p-methylstyrene, preferably 54% of ethylene content of ethylene propylene diene monomer, ENB as a third monomer, 10.5% of ENB, and is used for preparing brominated ethylene propylene rubber.
Example 3
The rubber compound comprises the following components in parts by mass:
37 parts of natural rubber, 38 parts of brominated isobutylene p-methylstyrene rubber, 25 parts of brominated ethylene propylene rubber, 7 parts of an activator, 4 parts of an anti-aging agent, 2 parts of a modifier, 52 parts of a reinforcing agent, 8 parts of a processing aid, 6 parts of a plasticizer and 4.5 parts of a vulcanization accelerator.
The preparation method comprises the following specific steps:
manufacturing equipment and key process parameters: the meshing internal mixer with the nominal volume of more than 90L has the temperature of the temperature control unit set within the range of 30-40 ℃ and the top plug pressure of 0.5 MPa. The rotor speed of the internal mixer in the following steps 1-5 is 35-45 r/min, and the rotor speed of the internal mixer in the steps 6-7 is 15-20 r/min.
S1, preparing brominated ethylene propylene rubber, mixing 1 g and 3 g of butadiene sulfone and a brominating agent N-1, 3-brominated-dimethylhexanoyl amide, dissolving in 50ml of ethyl acetate, and stirring until the mixture is completely dissolved to prepare liquid for later use;
s2, adding 30kg of ethylene propylene diene monomer into an internal mixer, mixing and heating to 40-50 ℃, adding the liquid to be used in the step 1, continuously mixing to 70 ℃, keeping for 1-2 min, and discharging to obtain ethylene propylene bromide rubber;
s3, putting natural rubber, brominated isobutylene p-methylstyrene rubber and brominated ethylene propylene rubber into an internal mixer, and mixing for 30-45S;
s4, adding the modifier and the reinforcing agent into an internal mixer, and mixing for 30-40S;
s5, putting the active agent and the anti-aging agent into an internal mixer together, and mixing for 45-60S;
s6, putting the plasticizer into an internal mixer, mixing to 130 ℃, and continuously mixing for 80-90S at the temperature of 130-135 ℃ by using an equipment temperature control module;
s7, discharging the rubber to a sheet discharging machine, performing air cooling to obtain master batch, and standing for more than 2 hours;
s8, putting the cooled and parked master batch into an internal mixer, and mixing for 30-40S;
and S9, adding a vulcanization accelerator into the internal mixer, mixing for 30-40S, lifting and lifting the internal mixer to a top bolt for 1 time, discharging the rubber when the mixture is mixed to 100 ℃, and cooling to obtain the low-temperature-resistant and aging-resistant rubber material.
Of these, in example 3, the natural rubber is preferably SMR 5L, preferably 0.75% of benzyl bromide of isobutylene p-methylstyrene is brominated, preferably the ethylene content of ethylene-propylene-diene monomer is 60%, and the third monomer content thereof is 10%, for the production of ethylene-propylene-bromide rubber.
Comparative example 1
A natural rubber aging-resistant rubber compound comprises the following components in parts by mass:
60 parts of natural rubber, 40 parts of butadiene rubber, 5 parts of an active agent, 5 parts of an anti-aging agent, 52 parts of a reinforcing agent, 4 parts of a processing aid, 6 parts of a plasticizer and 3 parts of a vulcanization accelerator.
The preparation method comprises the following specific steps:
manufacturing equipment and key process parameters: the meshing internal mixer with the nominal volume of more than 90L has the temperature of the temperature control unit set within the range of 30-40 ℃ and the top plug pressure of 0.5 MPa. The rotor speed of the internal mixer in the following steps 1-5 is 35-45 r/min, and the rotor speed of the internal mixer in the steps 6-7 is 15-20 r/min.
S1, putting the natural rubber and the butadiene rubber into an internal mixer, and mixing for 30-45S;
s2, putting the active agent, the anti-aging agent and the processing aid into an internal mixer, and mixing for 30-40S;
s3, putting the reinforcing agent into an internal mixer together, and mixing for 45-60S;
s4, putting the plasticizer into an internal mixer, and mixing to 130 ℃;
s5, discharging the rubber to a sheet discharging machine, performing air cooling to obtain master batch, and standing for more than 2 hours;
s6, putting the cooled and parked master batch into an internal mixer, and mixing for 30-40S;
and S7, adding a vulcanization accelerator into the internal mixer, mixing for 30-40S, lifting and lifting the mixture to a top bolt for 1 time, discharging the mixture when the mixture is mixed to 100 ℃, and cooling to obtain the rubber material of the natural rubber.
Comparative example 2
The chloroprene rubber aging-resistant rubber compound comprises the following components in parts by mass:
100 parts of chloroprene rubber, 7 parts of activator, 4 parts of anti-aging agent, 52 parts of reinforcing agent, 8 parts of processing aid, 6 parts of plasticizer and 4.5 parts of vulcanization accelerator.
The preparation method comprises the following specific steps:
manufacturing equipment and key process parameters: the meshing internal mixer with the nominal volume of more than 90L has the temperature of the temperature control unit set within the range of 30-40 ℃ and the top plug pressure of 0.5 MPa. The rotor speed of the internal mixer in the following steps 1-5 is 35-45 r/min, and the rotor speed of the internal mixer in the steps 6-7 is 15-20 r/min.
S1, feeding the chloroprene rubber and the activator into an internal mixer, and mixing for 30-45S;
s2, putting the anti-aging agent and the processing aid into an internal mixer, and mixing for 30-40S;
s3, putting the reinforcing agent into an internal mixer together, and mixing for 45-60S;
s4, putting the plasticizer into an internal mixer, and mixing to 110 ℃;
s5, discharging the rubber to a sheet discharging machine, performing air cooling to obtain master batch, and standing for more than 2 hours;
s6, putting the cooled and parked master batch into an internal mixer, and mixing for 30-40S;
and S7, putting the vulcanization accelerator into an internal mixer, mixing for 30-40S, lifting and lifting the mixture to a top bolt for 1 time, discharging the rubber when the mixture is mixed to 100 ℃, and cooling to obtain the chloroprene rubber aging-resistant rubber material.
The test standards and methods of rubber compounds and products are as follows:
1. mechanical property test of rubber compounds: the following performance tests were performed on the rubber compounds prepared in examples 1 to 5 and comparative example 1:
the hardness is tested according to GB/T531.1-2008 standard, the tensile strength, the stress at definite elongation and the elongation at break are tested according to GB/T528-.
The rubber compound test performance parameters corresponding to the above examples and comparative examples are shown in table 1:
TABLE 1 results of examining the Performance parameters of the rubber compounds of the examples and comparative examples
The data analysis in table 1 shows that the detection performance of the low-temperature-resistant and aging-resistant rubber compound provided by the invention can meet the technical requirements, and the data analysis in table 1 shows that when the total amount of raw rubber is 100 parts, referring to examples 1 to 3, the raw rubber comprises the following specific components in parts by mass: 35-40 parts of natural rubber, 35-40 parts of brominated isobutylene p-methylstyrene rubber and 20-30 parts of brominated ethylene propylene rubber, the rubber material performance of the prepared low-temperature-resistant and aging-resistant rubber material is obviously superior to that of the rubber materials prepared in comparative examples 1 and 2. Further, referring to Table 1, the low temperature brittleness temperature at low temperature indicates that the rubber compound has better low temperature resistance. Compared with the comparative example 1, the rubber compounds provided in the examples 1 to 3 have better ozone aging resistance and thermal aging resistance, and other properties such as low-temperature brittleness temperature and strength are similar. Compared with the comparative example 2, the rubber compounds provided in the examples 1 to 3 have better ozone aging resistance and low-temperature brittleness temperature, and similar strength, hardness and other properties. Examples 1 to 3 combine all the excellent properties of comparative example 1 and comparative example 2, and are perfectly compatible in aging resistance and low temperature resistance.
2. The mechanical performance test of the product is that the mechanical performance test of the air spring air bag made of the rubber compound is as follows:
a) and (3) normal temperature test: the transverse stiffness of the air spring bellows was measured at a vertical load Fz of 95kN, 140kN and a transverse amplitude dx, y of ± 40 mm. The loading speed V is 5 mm/s;
the vertical stiffness of the air spring is measured when the vertical load Fz is 95kN and 140kN and the vertical amplitude dz is +/-10 mm. The loading speed V is 5mm/s, and the additional air chamber Vd is 110L.
b) And (3) low-temperature test: respectively placing the products at a constant temperature of-50 ℃ for 48 hours, and measuring the vertical rigidity and the transverse rigidity of the products at various temperatures according to the procedure in the step a).
c) And (3) fatigue test: at-50 ℃ ambient temperature, 60 ten thousand torsional fatigue was performed, and the loading conditions were as follows.
d) Thermal aging test: placing the product in an environment box at 70 ℃ for 14 days, taking out the product, standing the product at 23 ℃ for 24 hours, and testing the vertical rigidity and the transverse rigidity of the product according to the procedure in the step a).
e) And (3) air tightness test: and filling the air spring with air pressure not lower than 850kPa at a standard height HT of 326mm, maintaining the pressure for 30s, reducing the pressure to be not lower than 615kPa, maintaining the pressure for 10min, measuring the pressure reduction of the air spring at 6min to 10min, and performing tests after respectively maintaining the temperature at normal temperature and at-50 ℃ for 48 h.
The detection performance parameters of the air spring air bags made of the rubber compounds in the embodiments 1-3 and the comparative examples 1 and 2 are shown in the table 2:
TABLE 2 results of performance testing of air spring products of examples and comparative examples
As can be seen from the "-50 ℃ transverse rigidity change rate and-50 ℃ air tightness" in the data of Table 2, the air spring airbags of examples 1-3 have superior performance compared with comparative examples 1-2, and the data thereof is determined by the better low-temperature characteristics of the rubber compound in accordance with the data of compression set and low-temperature brittleness temperature in the performance of the rubber compound in Table 1. In addition, other various performances of the air spring air bag in the embodiments 1-3 meet the technical requirements of products.
Example 4
The rubber compound comprises the following components in parts by mass:
40 parts of natural rubber, 40 parts of brominated isobutylene p-methylstyrene rubber, 20 parts of brominated ethylene propylene rubber, 7 parts of an active agent, 4 parts of an anti-aging agent, 3 parts of a modifier comprising 1.8 parts of a silane coupling agent, 40001.2 parts of PEG, 52 parts of a reinforcing agent, 8 parts of a processing aid comprising 3 parts of Koresin tackifying resin and 5 parts of aromatic hydrocarbon resin, 6 parts of a plasticizer, 4.5 parts of a vulcanization accelerator comprising 1.8 parts of sulfur, 0.8 part of alkyl dithiophosphate, 0.7 part of dicumyl peroxide and 1.2 parts of N-cyclohexyl-2-benzothiazole sulfonamide.
The preparation method comprises the following specific steps:
manufacturing equipment and key process parameters: the meshing internal mixer with the nominal volume of more than 90L has the temperature of the temperature control unit set within the range of 30-40 ℃ and the top plug pressure of 0.5 MPa. The rotor speed of the internal mixer in the following steps 1-5 is 35-45 r/min, and the rotor speed of the internal mixer in the steps 6-7 is 15-20 r/min.
S1, preparing brominated ethylene propylene rubber, mixing 1 g and 3 g of butadiene sulfone and a brominating agent N-1, 3-brominated-dimethylhexanoyl amide, dissolving in 50ml of ethyl acetate, and stirring until the mixture is completely dissolved to prepare liquid for later use;
s2, adding 30kg of ethylene propylene diene monomer into an internal mixer, mixing and heating to 40-50 ℃, adding the liquid to be used in the step 1, continuously mixing to 70 ℃, keeping for 1-2 min, and discharging to obtain ethylene propylene bromide rubber;
s3, putting natural rubber, brominated isobutylene p-methylstyrene rubber and brominated ethylene propylene rubber into an internal mixer, and mixing for 30-45S;
s4, adding the modifier and the reinforcing agent into an internal mixer, and mixing for 30-40S;
s5, putting the active agent and the anti-aging agent into an internal mixer together, and mixing for 45-60S;
s6, putting the plasticizer into an internal mixer, mixing to 130 ℃, and continuously mixing for 80-90S at the temperature of 130-135 ℃ by using an equipment temperature control module;
s7, discharging the rubber to a sheet discharging machine, performing air cooling to obtain master batch, and standing for more than 2 hours;
s8, putting the cooled and parked master batch into an internal mixer, and mixing for 30-40S;
and S9, adding a vulcanization accelerator into the internal mixer, mixing for 30-40S, lifting and lifting the internal mixer to a top bolt for 1 time, discharging the rubber when the mixture is mixed to 100 ℃, and cooling to obtain the low-temperature-resistant and aging-resistant rubber material.
Comparative example 3
The parts by weight of each component added in comparative example 3 were the same as in example 4 except that step S3 and step S4 were different in the preparation method, specifically:
s3, putting the activator and the antioxidant S4 into an internal mixer, and mixing for 30-40S;
and S4, putting the modifier and the reinforcing agent into an internal mixer together, and mixing for 45-60S.
The following performance tests were carried out on the rubber compounds prepared in example 4 and comparative example 3:
the hardness is tested according to GB/T531.1-2008 standard, the tensile strength, the stress at definite elongation and the elongation at break are tested according to GB/T528-.
The rubber compound test performance parameters for example 4 and comparative example 3 are shown in table 3:
table 3 results of testing performance parameters for the rubber compounds of example 4 and comparative example 3
As can be seen from Table 3, the rubber compound of example 4 is superior in properties to the rubber compound obtained in comparative example 3, in which ozone aging resistance, tensile strength and elongation at break are outstanding. Example 4 differs from comparative example 3 only in that, in the preparation, after step S2 is completed, the modifier and the reinforcing agent are added, and then the activator and the antioxidant are added. Specifically, the preparation method of example 4 has the beneficial effects that the modifier and the reinforcing agent are added to be in full contact with the rubber substrate, on one hand, the addition of the modifier increases the mixing uniformity of the three rubbers in the step S1, and chemical groups for enhancing the reactivity, such as hydroxyl groups and free sulfur radicals, are further grafted on the molecular chain terminal groups of the rubber substrate, so that the affinity between the rubber substrate and the reinforcing agent is enhanced, the reinforcing effect of the reinforcing agent is enhanced, and meanwhile, the bonding difference of different rubber substrates to the reinforcing agent is reduced, so that the reinforcing agent is more uniformly dispersed in different rubber substrates; and the activator and the anti-aging agent are added and mixed, so that the reinforcing agent can be effectively prevented from generating adsorption on the activator and the anti-aging agent before being mixed into the rubber matrix, and the activation effect and the anti-aging effect are influenced. In conclusion, the rubber material prepared by the preparation method provided by the invention has excellent low temperature resistance and aging resistance, the mechanical properties of the product meet the requirements of the standard TB/T2841-.
Claims (12)
1. The low-temperature-resistant and aging-resistant rubber compound is characterized by comprising the following components in parts by weight: 100 parts of raw rubber, 7 parts of an active agent, 4 parts of an anti-aging agent, 1-3 parts of a modifier, 52 parts of a reinforcing agent, 8 parts of a processing aid, 6 parts of a plasticizer and 4.5 parts of a vulcanization accelerator; the raw rubber comprises rubber A, rubber B and rubber C, wherein the rubber A is natural rubber, the rubber B is brominated isobutylene p-methylstyrene rubber or chloroprene rubber or brominated butyl rubber, the rubber C is brominated ethylene propylene rubber, and the brominated ethylene propylene rubber is obtained by bromination modification of ethylene propylene diene monomer.
2. The low-temperature-resistant and aging-resistant rubber compound according to claim 1, wherein the rubber B is brominated isobutylene p-methylstyrene rubber, and the raw rubber comprises the following specific components in parts by mass: 35-40 parts of natural rubber, 35-40 parts of brominated isobutylene p-methylstyrene rubber and 20-30 parts of brominated ethylene propylene rubber.
3. The low temperature and aging resistant rubber compound according to claim 1,
the natural rubber is smoked sheet rubber or SMR 5L;
0.75% of benzyl bromide of the brominated isobutylene p-methylstyrene;
the ethylene content of the ethylene-propylene-diene monomer rubber is 53-67%, and the content of a third monomer of the ethylene-propylene-diene monomer rubber is 9-11%.
4. The low temperature and aging resistant rubber compound according to claim 3, wherein the natural rubber is a smoked sheet rubber RSS 1; the ethylene-propylene-diene monomer rubber has a vinyl content of 54 percent, the third monomer of the ethylene-propylene-diene monomer rubber is ENB, and the ENB content is 10.5 percent.
5. The low-temperature-resistant and aging-resistant rubber compound according to claim 1, wherein the active agent comprises the following specific components in parts by mass: 5 parts of zinc oxide and 2 parts of stearic acid.
6. The low-temperature-resistant and aging-resistant rubber compound according to claim 1, wherein the anti-aging agent comprises the following specific components in parts by mass: 40201 parts, RD 1 part, and paraffin wax 2 parts.
7. The low-temperature-resistant and aging-resistant rubber compound according to claim 1, wherein the reinforcing agent comprises the following specific components in parts by mass: 34 parts of carbon black and 18 parts of white carbon black.
8. The low temperature and aging resistant rubber compound according to claim 7, wherein the white carbon black is preferably a rubber compound having a specific surface area of more than 150m2White carbon black in a ratio of/g.
9. The low-temperature aging resistant rubber compound according to claim 7, wherein the modifier comprises a silane coupling agent, and the mass of the silane coupling agent is 10% of the mass of the white carbon black.
10. The low temperature and aging resistant rubber compound of claim 1, wherein the processing aid comprises a Koresin tackifying resin and an aromatic hydrocarbon resin, and the plasticizer is a paraffin oil.
11. The low temperature and aging resistant rubber compound according to claim 1, wherein the vulcanization accelerator comprises sulfur, alkyl dithiophosphate, dicumyl peroxide, N-cyclohexyl-2-benzothiazole sulfenamide.
12. The preparation method of the low-temperature-resistant and aging-resistant rubber compound is characterized by comprising the following steps of:
s1, preparing brominated ethylene propylene rubber, mixing 1 g and 3 g of butadiene sulfone and a brominating agent N-1, 3-brominated-dimethylhexanamide, dissolving in 50ml of ethyl acetate, and stirring until the mixture is completely dissolved to prepare liquid for later use;
s2, adding 30kg of ethylene propylene diene monomer into an internal mixer, mixing and heating to 40-50 ℃, adding the liquid to be used in the step 1, continuously mixing to 70 ℃, keeping for 1-2 min, and discharging to obtain ethylene propylene bromide rubber;
s3, putting the natural rubber, the rubber B and the ethylene propylene bromide rubber into an internal mixer, and mixing for 30-45S;
s4, adding the modifier and the reinforcing agent into an internal mixer, and mixing for 30-40S;
s5, putting the active agent and the anti-aging agent into an internal mixer together, and mixing for 45-60S;
s6, putting the plasticizer into an internal mixer, mixing to 130 ℃, and continuously mixing for 80-90S at the temperature of 130-135 ℃ by using an equipment temperature control module;
s7, discharging the rubber to a sheet discharging machine, performing air cooling to obtain master batch, and standing for more than 2 hours;
s8, putting the cooled and parked master batch into an internal mixer, and mixing for 30-40S;
and S9, adding a vulcanization accelerator into the internal mixer, mixing for 30-40S, lifting and lifting the internal mixer to a top bolt for 1 time, discharging the rubber when the mixture is mixed to 100 ℃, and cooling to obtain the low-temperature-resistant and aging-resistant rubber material.
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| CN106608990A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Rubber composition and preparation method thereof, and vulcanized rubber |
| US20170158845A1 (en) * | 2015-12-04 | 2017-06-08 | Sumitomo Rubber Industries, Ltd. | Rubber composition for tire and pneumatic tire |
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