CN111548539B - Rubber material for elastic joint and preparation method thereof - Google Patents
Rubber material for elastic joint and preparation method thereof Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 99
- 239000005060 rubber Substances 0.000 title claims abstract description 99
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 42
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 42
- 229920001194 natural rubber Polymers 0.000 claims abstract description 42
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 32
- 239000003063 flame retardant Substances 0.000 claims abstract description 23
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 19
- 239000003607 modifier Substances 0.000 claims abstract description 18
- 239000004014 plasticizer Substances 0.000 claims abstract description 13
- 239000013543 active substance Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims description 47
- 239000006229 carbon black Substances 0.000 claims description 45
- 238000007599 discharging Methods 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 13
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 13
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012188 paraffin wax Substances 0.000 claims description 12
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical group C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 abstract description 22
- 238000012360 testing method Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000003068 static effect Effects 0.000 description 8
- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000009975 flexible effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005063 High cis polybutadiene Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- REQPQFUJGGOFQL-UHFFFAOYSA-N dimethylcarbamothioyl n,n-dimethylcarbamodithioate Chemical compound CN(C)C(=S)SC(=S)N(C)C REQPQFUJGGOFQL-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009661 fatigue test Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- HNWAHFPYJHAAJE-UHFFFAOYSA-N n-tert-butyl-1,3-benzothiazole-2-sulfonamide Chemical group C1=CC=C2SC(S(=O)(=O)NC(C)(C)C)=NC2=C1 HNWAHFPYJHAAJE-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- 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)
- 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 discloses a rubber material for an elastic node, which comprises the following components in parts by mass: 60-75 parts of natural rubber, 25-40 parts of solution-polymerized styrene-butadiene rubber, 50-60 parts of reinforcing agent, 5-10 parts of active agent, 4-8 parts of anti-aging agent, 2-3.5 parts of modifier, 3-8 parts of flame retardant, 5-12 parts of plasticizer, 1.5-3 parts of vulcanizing agent and 1.5-3 parts of accelerator, wherein the sum of the parts by mass of the natural rubber and the solution-polymerized styrene-butadiene rubber is 100 parts. The technical problem that the rubber material for the elastic node in the prior art cannot meet the standard requirement of combustion performance is solved.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a rubber material for an elastic node and a preparation method thereof.
Background
Modern railway vehicles use a large number of various rubber elastic elements in the parts of suspension systems, equipment mounting systems, connections, limiting and the like to play roles of vibration reduction, buffering, flexible connection, limiting and the like. However, rubber in the elements belongs to flammable materials, once a fire disaster occurs, rubber materials can be combusted and emit a large amount of heat and smoke, and the smoke often has certain toxicity, so that people are not easy to evacuate and escape when a vehicle is in the fire disaster, and fire safety hazards in the fire disaster are increased.
The european union issued fire protection standard EN45545-2 for railway vehicles in 2013. At present, many countries adopt this standard to regulate the requirements of the fire-resistance of materials and components for railway vehicles, which puts definite requirements on the combustion properties of rubber-elastic elements.
The elastic node is an elastic connector formed by vulcanizing and compounding rubber and metal pieces, plays roles of flexible connection and buffering, and is an important elastic element on a railway vehicle. The method is widely applied to subway vehicles, urban light rail vehicles and motor train unit high-speed trains. There are strict requirements on the fire protection properties of the resilient node.
However, it is difficult to satisfy both the mechanical property requirements and the flammability requirements of the rubber material. In the prior art, a large amount of flame retardants (aluminum hydroxide, zinc borate, antimony trioxide and the like which account for 90 parts by mass) are added into natural rubber to ensure that the burning performance of rubber materials meets the requirements of EN 45545-2R 9 HL 2; although the flame retardant antimony trioxide used in the technology has a very obvious effect on improving the flame retardance of the rubber material, the flame retardant antimony trioxide belongs to a substance which is forbidden in the railway industry, and the mass ratio of the antimony trioxide is about 3100mg/kg and exceeds a limit value of 1000mg/kg according to the dosage disclosed in the prior art. Therefore, the rubber material is prepared, so that the body of the rubber material can reach the combustion performance required by the standard EN 45545-2R 9 HL2, does not contain any forbidden substance, and is the most fundamental solution.
Disclosure of Invention
The invention aims to provide a rubber material for an elastic node and a preparation method thereof, and aims to solve the technical problem that the rubber material for the elastic node in the prior art cannot meet the standard requirement of combustion performance.
In order to realize the purpose, the invention adopts the following technical scheme:
a rubber material for elastic joints comprises the following components in parts by mass:
60-75 parts of natural rubber, 25-40 parts of solution-polymerized styrene-butadiene rubber, 50-60 parts of reinforcing agent, 5-10 parts of active agent, 4-8 parts of anti-aging agent, 2-3.5 parts of modifier, 3-8 parts of flame retardant, 5-12 parts of plasticizer, 1.5-3 parts of vulcanizing agent and 1.5-3 parts of accelerator, wherein the sum of the parts by mass of the natural rubber and the solution-polymerized styrene-butadiene rubber is 100 parts.
Preferably, the composition comprises the following components in parts by mass:
75 parts of natural rubber, 25 parts of solution-polymerized styrene-butadiene rubber, 50-60 parts of reinforcing agent, 5-10 parts of active agent, 4-8 parts of anti-aging agent, 2-3.5 parts of modifier, 3-8 parts of flame retardant, 5-12 parts of plasticizer, 1.5-3 parts of vulcanizing agent and 1.5-3 parts of accelerator, wherein the sum of the parts by weight of the natural rubber and the solution-polymerized styrene-butadiene rubber is 100 parts.
Preferably, the solution polymerized styrene-butadiene rubber is preferably a solution polymerized styrene-butadiene rubber with a styrene content of 15% and a vinyl content of 30%.
Preferably, the reinforcing agent comprises 20-30 parts of white carbon black and carbon black.
Preferably, the white carbon black is preferably that the specific surface area of the white carbon black is more than 110m2White carbon black in a ratio of/g.
Preferably, the flame retardant is ammonium polyphosphate.
Preferably, the flame retardant is high molecular weight crystal form II ammonium polyphosphate modified by microencapsulation surface coating.
Preferably, the vulcanizing agent is sulfur and N, N' -m-phenylene bismaleimide, and the accelerator is N-tert-butyl-2-benzothiazole sulfonamide and tetrabenzyl thiuram disulfide.
Preferably, the composition comprises the following components in parts by mass:
75 parts of natural rubber, 25 parts of solution-polymerized styrene-butadiene rubber, 3.5 parts of zinc oxide, 1.5 parts of stearic acid, 30 parts of white carbon black, 30 parts of carbon black, 3 parts of anti-aging agent 4010NA, 2 parts of anti-aging agent RD, 3 parts of paraffin, 3.5 parts of modifier, 12 parts of naphthenic oil, 8 parts of high molecular weight crystal form-II ammonium polyphosphate, 1 part of sulfur, 0.5 part of N, N' -m-phenylene bismaleimide, 1 part of accelerator TBzTD and 2 parts of accelerator TBBS.
A preparation method of a rubber compound for elastic joints comprises the following steps:
step 1: putting natural rubber and solution polymerized styrene butadiene rubber into an internal mixer, and mixing for 45-50 s;
step 2: putting the active agent, the anti-aging agent RD and paraffin into an internal mixer, and mixing for 30-40 s;
and step 3: putting the modifier, the reinforcing agent and the flame retardant into an internal mixer together, and mixing for 55-65 s;
and 4, step 4: putting the anti-aging agent 4010NA and the plasticizer into an internal mixer, mixing to 143 ℃, and continuously mixing for 75-90 s at the temperature of 143-153 ℃ by using an equipment temperature control module;
and 5: discharging the rubber, discharging the rubber to a sheet discharging machine, performing air cooling to obtain master batch, and standing for more than 2 hours;
step 6: putting the cooled and parked master batch into an internal mixer, and mixing for 35-40 s;
and 7: and (3) putting a vulcanizing agent and an accelerant into an internal mixer, mixing for 40-50 s, lifting and lifting a top plug for 1 time, continuously mixing to 105 ℃, discharging rubber, discharging a piece from a piece discharging machine, and performing air cooling to obtain the fireproof rubber material for the elastic node.
Compared with the prior art, the invention has the advantages and beneficial effects that:
the rubber compound suitable for the elastic node is prepared by mixing natural rubber and solution-polymerized styrene-butadiene rubber and reasonably and optimally matching the natural rubber, the reinforcing agent and the flame retardant, and the prepared rubber compound for the elastic node also meets the requirement of combustion performance on the premise of meeting various mechanical properties by utilizing the rubber compound, namely the combustion performance meets the requirement of EN 45545-2R 9 HL2, and the mechanical property also meets the requirement of the standard TB/T2843-. Therefore, the requirements of the standard EN 45545-2R 9 HL2 grade can be met without adding a large amount of flame retardant. The technical problem that the rubber material for the elastic node in the prior art cannot meet the standard requirement of combustion performance is solved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The rubber compound suitable for the elastic node is prepared by mixing natural rubber and solution-polymerized styrene-butadiene rubber and reasonably and optimally matching the natural rubber, the reinforcing agent and the flame retardant, and the prepared rubber compound for the elastic node also meets the requirement of combustion performance on the premise of meeting various mechanical properties by utilizing the rubber compound, namely the combustion performance meets the requirement of EN 45545-2R 9 HL2, and the mechanical property also meets the requirement of the standard TB/T2843-. Therefore, the requirements of the standard EN 45545-2R 9 HL2 grade can be met without adding a large amount of flame retardant. The technical problem that the rubber material for the elastic node in the prior art cannot meet the standard requirement of combustion performance is solved.
Specifically, the coating comprises the following components in parts by mass:
60-75 parts of natural rubber, 25-40 parts of solution-polymerized styrene-butadiene rubber, 50-60 parts of reinforcing agent, 5-10 parts of active agent, 4-8 parts of anti-aging agent, 2-3.5 parts of modifier, 3-8 parts of flame retardant, 5-12 parts of plasticizer, 1.5-3 parts of vulcanizing agent and 1.5-3 parts of accelerator, wherein the sum of the parts by mass of the natural rubber and the solution-polymerized styrene-butadiene rubber is 100 parts.
In a preferred embodiment, 75 parts of natural rubber and 25 parts of solution polymerized styrene butadiene rubber are used.
Further, the natural rubber can be selected from standard rubber or smoked sheet rubber; the natural rubber is preferably smoked sheet rubber.
In a preferred embodiment, the solution polymerized styrene-butadiene rubber preferably has a styrene content of 15% and a vinyl content of 30%.
Specifically, the styrene-butadiene rubber and the natural rubber have similar molecular main chain structures, are diolefin rubber, have similar polarities and have very good compatibility. The solution polymerized styrene-butadiene rubber has a plurality of grades because of molecular design during synthesis, and the commercialized grade has the styrene content of between 10 and 40 percent and the vinyl content of between 10 and 80 percent. When the optimized solution polymerized styrene-butadiene rubber is a grade with low styrene and medium-low vinyl content, the glass transition temperature Tg is approximately equal to-65 ℃, so that the solution polymerized styrene-butadiene rubber with the grade has better low-temperature performance. Compared with emulsion polymerized styrene butadiene rubber, the solution polymerized styrene butadiene rubber has higher cis-1, 4-structure content in the molecule and better rebound resilience. As the content of styrene in the solution-polymerized styrene-butadiene rubber is increased, the steric hindrance effect of the movement relaxation of the polymer chain is increased, the hysteresis loss is increased, and the influence of the vinyl content on the hysteresis performance of the rubber material is not obvious. Therefore, the preferred solution-polymerized styrene-butadiene rubber has a lower hysteresis loss. The low-temperature performance and elasticity of the solution polymerized styrene-butadiene rubber are close to those of natural rubber. In addition, the thermal degradation temperature resistance and the aging resistance of the rubber are better than those of natural rubber. The solution polymerized styrene-butadiene rubber replaces partial natural rubber to be used together, thereby playing a good role in blending and modifying and improving the performance of rubber materials. The solution polymerized styrene-butadiene rubber reduces the proportion of natural rubber in the rubber material and improves the heat resistance and the thermal decomposition temperature of the rubber material. The rubber material can form a continuous compact carbon layer after being burnt, and can play a better heat insulation protection role on the unburned polymer at the lower layer, thereby improving the burning performance of the rubber.
In a preferred embodiment, the reinforcing agent comprises white carbon black and carbon black; 20-30 parts of white carbon black. The white carbon black can be used in the amount of 20, 22, 25, 28, 30 and the like. Specifically, the white carbon black has the synergistic effects of reinforcement and flame retardance, and can improve the mechanical property and the combustion property of the rubber material. In addition, besides the blending ratio of the carbon black and the white carbon black needs to be controlled, the selection of the specific surface area and the dispersion characteristic of the white carbon black is also critical, and the specific surface area needs to be controlled at 110m2More than g and has high dispersion property. To obtain good dispersing effect and mechanical properties.
In a preferred embodiment, the flame retardant is ammonium polyphosphate. The addition of a small amount of ammonium polyphosphate hardly affects the mechanical properties of the rubber material, but can play a role in stabilizing char formation and preventing a combustion layer from cracking during combustion. The char layer formed during combustion protects the underlying unburned polymer. And the ammonium polyphosphate is preferably a high molecular weight crystal form-II ammonium polyphosphate which is modified by microencapsulation surface coating.
Further, the plasticizer is naphthenic oil. Naphthenic oil is a common plasticizer for natural rubber, and although the naphthenic oil belongs to a small-molecular combustible substance, the naphthenic oil has little influence on the combustion performance of rubber materials when used in a small amount. Active agents include zinc oxide and stearic acid; the anti-aging agent is prepared by using 4010NA, RD and paraffin in combination; the modifier is a silane coupling agent, and the specific amount of the modifier is 10% of the using amount of the white carbon black.
In a preferred embodiment, the vulcanizing agent is preferably sulfur and N, N' -m-phenylene bismaleimide, and the accelerator is preferably N-tert-butyl-2-benzothiazole sulfenamide and tetrabenzyl thiuram dithio.
In order to better illustrate a rubber compound for an elastic node and a method for preparing the same, reference will now be made in detail with reference to comparative examples and examples.
Comparative example
A rubber compound for an elastic node comprises the following components in parts by mass:
90 parts of natural rubber, 10 parts of high cis-polybutadiene rubber, 50 parts of carbon black, 12 parts of white carbon black, 8 parts of zinc oxide, 2 parts of stearic acid, 40102 parts of an anti-aging agent, 1 part of an anti-aging agent RD, 2.5 parts of paraffin, 1.2 parts of a silane coupling agent, 7 parts of naphthenic oil, 1.7 parts of sulfur, 0.4 part of an accelerator TMTM and 1.5 parts of an accelerator TBBS.
Example 1
A rubber compound for an elastic node comprises the following components in parts by mass:
75 parts of natural rubber, 25 parts of solution-polymerized styrene-butadiene rubber, 3.5 parts of zinc oxide, 1.5 parts of stearic acid, 30 parts of white carbon black, 30 parts of carbon black, 3 parts of anti-aging agent 4010NA, 2 parts of anti-aging agent RD, 3 parts of paraffin, 3.5 parts of modifier, 12 parts of naphthenic oil, 8 parts of high molecular weight crystal form-II ammonium polyphosphate, 1 part of sulfur, 0.5 part of N, N' -m-phenylene bismaleimide, 1 part of accelerator TBzTD and 2 parts of accelerator TBBS.
The preparation method comprises the following specific steps:
manufacturing equipment and key process parameters: a meshing internal mixer with a nominal volume (90-250) L is provided, the temperature of a temperature control unit is set within a range of 30-40 ℃, and the top plug pressure is 0.45-0.6 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.
Step 1: putting natural rubber and solution polymerized styrene butadiene rubber into an internal mixer, and mixing for 45-50 s;
step 2: putting the active agent, the anti-aging agent RD and paraffin into an internal mixer, and mixing for 30-40 s;
and step 3: putting the modifier, the reinforcing agent and the flame retardant into an internal mixer together, and mixing for 55-65 s;
and 4, step 4: putting the anti-aging agent 4010NA and the plasticizer into an internal mixer, mixing to 143 ℃, and continuously mixing for 75-90 s at the temperature of 143-153 ℃ by using an equipment temperature control module;
and 5: discharging the rubber, discharging the rubber to a sheet discharging machine, performing air cooling to obtain master batch, and standing for more than 2 hours;
step 6: putting the cooled and parked master batch into an internal mixer, and mixing for 35-40 s;
and 7: and (3) putting a vulcanizing agent and an accelerant into an internal mixer, mixing for 40-50 s, lifting and lifting a top plug for 1 time, continuously mixing to 105 ℃, discharging rubber, discharging the rubber, discharging a piece from a piece discharging machine, and performing air cooling to obtain the fireproof rubber material for the elastic node.
Example 2
A rubber compound for an elastic node comprises the following components in parts by mass:
70 parts of natural rubber, 30 parts of solution polymerized styrene butadiene rubber, 5 parts of zinc oxide, 2 parts of stearic acid, 25 parts of white carbon black, 30 parts of carbon black, 2.5 parts of anti-aging agent 4010NA, 1 part of anti-aging agent RD, 2 parts of paraffin, 2.5 parts of modifier, 8 parts of naphthenic oil, 5 parts of high molecular weight crystal form-II ammonium polyphosphate, 1.3 parts of sulfur, 0.8 part of N, N' -m-phenylene bismaleimide, 0.6 part of accelerator TBzTD and 1.6 parts of accelerator TBBS.
Manufacturing equipment and key process parameters: a meshing internal mixer with a nominal volume (90-250) L is provided, the temperature of a temperature control unit is set within a range of 30-40 ℃, and the top plug pressure is 0.45-0.6 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.
Step 1: putting natural rubber and solution polymerized styrene butadiene rubber into an internal mixer, and mixing for 45-50 s;
step 2: putting the active agent, the anti-aging agent RD and paraffin into an internal mixer, and mixing for 30-40 s;
and step 3: putting the modifier, the reinforcing agent and the flame retardant into an internal mixer together, and mixing for 55-65 s;
and 4, step 4: putting the anti-aging agent 4010NA and the plasticizer into an internal mixer, mixing to 143 ℃, and continuously mixing for 75-90 s at the temperature of 143-153 ℃ by using an equipment temperature control module;
and 5: discharging the rubber, discharging the rubber to a sheet discharging machine, performing air cooling to obtain master batch, and standing for more than 2 hours;
step 6: putting the cooled and parked master batch into an internal mixer, and mixing for 35-40 s;
and 7: and (3) putting a vulcanizing agent and an accelerant into an internal mixer, mixing for 40-50 s, lifting and lifting a top plug for 1 time, continuously mixing to 105 ℃, discharging rubber, discharging the rubber, discharging a piece from a piece discharging machine, and performing air cooling to obtain the fireproof rubber material for the elastic node.
Example 3
A rubber compound for an elastic node comprises the following components in parts by mass:
60 parts of natural rubber, 40 parts of solution polymerized styrene-butadiene rubber, 8 parts of zinc oxide, 2 parts of stearic acid, 20 parts of white carbon black, 30 parts of carbon black, 1.5 parts of anti-aging agent 4010NA, 1 part of anti-aging agent RD, 1.5 parts of paraffin, 2 parts of modifier, 5 parts of naphthenic oil, 3 parts of high molecular weight crystal form-II ammonium polyphosphate, 2 parts of sulfur, 1 part of N, N' -m-phenylene bismaleimide, 0.3 part of accelerator TBzTD and 1.2 parts of accelerator TBBS.
Manufacturing equipment and key process parameters: a meshing internal mixer with a nominal volume (90-250) L is provided, the temperature of a temperature control unit is set within a range of 30-40 ℃, and the top plug pressure is 0.45-0.6 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.
Step 1: putting natural rubber and solution polymerized styrene butadiene rubber into an internal mixer, and mixing for 45-50 s;
step 2: putting the active agent, the anti-aging agent RD and paraffin into an internal mixer, and mixing for 30-40 s;
and step 3: putting the modifier, the reinforcing agent and the flame retardant into an internal mixer together, and mixing for 55-65 s;
and 4, step 4: putting the anti-aging agent 4010NA and the plasticizer into an internal mixer, mixing to 143 ℃, and continuously mixing for 75-90 s at the temperature of 143-153 ℃ by using an equipment temperature control module;
and 5: discharging the rubber, discharging the rubber to a sheet discharging machine, performing air cooling to obtain master batch, and standing for more than 2 hours;
step 6: putting the cooled and parked master batch into an internal mixer, and mixing for 35-40 s;
and 7: and (3) putting a vulcanizing agent and an accelerant into an internal mixer, mixing for 40-50 s, lifting and lifting a top plug for 1 time, continuously mixing to 105 ℃, discharging rubber, discharging the rubber, discharging a piece from a piece discharging machine, and performing air cooling to obtain the fireproof rubber material for the elastic node.
Examples 4 to 7 are different from example 2 in the blending ratio between the natural rubber and the solution-polymerized styrene-butadiene rubber.
The test standard and method of the rubber compound and the product used for the elastic node are as follows:
1. mechanical property test of rubber compounds:
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-.
2. And (3) testing the combustion performance: maximum average heat release rate MARHE, maximum specific optical density DS maxToxicity index CITGThe radiant heat flux was 25kW/m as measured according to standards ISO5660-1, ISO5659-2 cited in EN45545-2:2013, respectively2。
3. And (3) testing the mechanical properties of the product:
a) radial stiffness test:
applying radial load to the elastic node at the ambient temperature of 23 ℃, repeating for 3 cycles, wherein the loading range is as follows: 0 kN-110 kN-0 kN, the speed is 5mm/min, the curve of the 3 rd cycle is recorded, and a point with the load of 85kN is found in the rising stage of the curve, so that the static radial stiffness of the elastic node when the load is 85kN is calculated;
b) axial stiffness test: applying axial load to the elastic node at the ambient temperature of 23 ℃, repeating for 3 cycles, wherein the loading range is as follows: 0 kN-6 kN-0 kN, the speed is 2mm/min, the curve of the 3 rd cycle is recorded, and a point with the load of 3.9kN is found in the rising stage of the curve, so that the static axial stiffness of the elastic node when the load is 3.9kN is calculated;
c) high and low temperature tests: and (3) after the elastic joint is respectively placed at the constant temperature of minus 25 ℃ and 50 ℃ for 24 hours, measuring the static radial stiffness and the static axial stiffness of the elastic joint at each temperature according to the procedures in a) and b).
d) Thermal aging test: and (3) placing the elastic node in an environment box at 70 ℃ for 14 days, taking out the elastic node, standing the elastic node in an environment at 23 ℃ for 24 hours, and testing the static radial rigidity and the static axial rigidity of the elastic node according to the procedures in a) and b).
e) And (3) fatigue test: and (3) radially loading +/-85 kN on the elastic node at the ambient temperature of 23 ℃, circulating for 300 ten thousand times under the condition of frequency of 1-3 Hz, and testing the fatigue static radial stiffness and the static axial stiffness of the elastic node according to the procedures in a) and b) after the test is finished.
TABLE 1 comparison of mechanical Properties of comparative and example compounds
TABLE 2 comparative flammability data for comparative and example compounds
TABLE 3 comparative and example elastic node product Performance comparative data
It can be seen from table 1 that as the amount of solution polymerized styrene butadiene rubber increases and the amount of natural rubber decreases, the tensile strength of the rubber compound gradually decreases. As can be seen from tables 1 and 2, when the total amount of crude rubber is 100 parts and the addition amount of the solution-polymerized styrene-butadiene rubber is 15 parts, the combustion performance of the obtained rubber material still cannot meet the requirements of the technical standards, so that the technical requirements cannot be met until the content of the solution-polymerized styrene-butadiene rubber reaches a certain value; meanwhile, it can be seen that when the addition amount of the solution polymerized styrene-butadiene rubber reaches 45 parts, the mechanical property of the obtained rubber material cannot meet the technical standard requirement of mechanical property, so that the mechanical property and the combustion property of the rubber material can meet the technical requirement at the same time by reasonably matching the two rubbers. As can be seen from tables 1 and 2, when the total amount of raw rubber is 100 parts, the content of natural rubber is 60-75 parts, and the dosage of the solution polymerized styrene-butadiene rubber is 25-40 parts, the prepared rubber material for the elastic node can simultaneously meet the requirements of mechanical property and combustion property of the rubber material.
Further, as can be seen from table 2, the comparative example cannot meet the burning performance of the rubber material, however, according to the invention, the solution polymerized styrene-butadiene rubber and the natural rubber are used together, the reinforcing agent adopts carbon black and white carbon black, the ammonium polyphosphate is used as the flame retardant, and the reasonable optimization and matching are performed among the components, so that the rubber material of the elastic node in the invention can meet the requirements of the burning performance EN 45545-2R 9 HL2 on the premise of meeting the technical requirements of the mechanical performance, thereby solving the problem that the burning performance of the rubber material for the elastic node in the prior art cannot meet the requirements of EN 45545-2R 9 HL 2.
Further, as can be seen from table 3, when the selected natural rubber content is 60-75 parts and the amount of the solution polymerized styrene-butadiene rubber is 25-40 parts, not only the obtained rubber material can meet the technical requirements of mechanical properties and combustion properties, but also the prepared elastic node product meets the technical requirements of product rigidity.
Example 8
In this embodiment, based on example 3, the blending ratio of carbon black and white carbon black of the reinforcing agent in the components is further analyzed, so that the ratio of carbon black to white carbon black is more reasonable, and thus a rubber compound with more excellent comprehensive properties is obtained, as shown in table 4 specifically:
table 4 Performance test results of rubber compounds with different amounts of carbon black and white carbon black
In Table 4, No. 1# -6# are 6 different test formulations, in which the blending ratio of carbon black and silica is changed only, and the other components are the same as those in example 3. As can be seen from Table 4, on the premise of keeping the hardness of the rubber compound basically consistent, the tensile strength, the elongation at break, the tear strength and the compression set of the rubber compound are slightly increased along with the increase of the using amount of the white carbon black, the change of other mechanical properties is not obvious, and the MARHE and D in the combustion performance indexesS maxThe improvement is gradual. When the using amount of the white carbon black reaches 35 parts, the ozone aging resistance and the cracking resistance are realized, because the white carbon black has an adsorption effect on the anti-aging agent, the more the white carbon black is used, the more the anti-aging agent is adsorbed, and the insufficient anti-aging agent is not transferred to the surface of the rubber to play a protection role, so that the cracking resistance of the rubber is realized. In addition, for rubber elastic elements such as elastic nodes, the smaller the compression set, the better, so in the case of combustion performance that can meet the technical requirements, the smaller the amount of white carbon black, the better. Therefore, the reinforcing agent is used in 50-60 parts, and when the white carbon black is used in 20-30 parts, the performance of the rubber material can meet the requirements of various technical indexes.
Claims (8)
1. The rubber material for the elastic node is characterized by comprising the following components in parts by mass:
60-75 parts of natural rubber, 25-40 parts of solution-polymerized styrene-butadiene rubber, 50-60 parts of reinforcing agent, 5-10 parts of active agent, 4-8 parts of anti-aging agent, 2-3.5 parts of modifier, 3-8 parts of flame retardant, 5-12 parts of plasticizer, 1.5-3 parts of vulcanizing agent and 1.5-3 parts of accelerator, wherein the sum of the parts by mass of the natural rubber and the solution-polymerized styrene-butadiene rubber is 100 parts, and the flame retardant is high-molecular-weight crystal form-II ammonium polyphosphate subjected to microencapsulation surface coating modification.
2. The rubber compound for the elastic joint as claimed in claim 1, characterized by comprising the following components in parts by mass:
75 parts of natural rubber, 25 parts of solution-polymerized styrene-butadiene rubber, 50-60 parts of reinforcing agent, 5-10 parts of active agent, 4-8 parts of anti-aging agent, 2-3.5 parts of modifier, 3-8 parts of flame retardant, 5-12 parts of plasticizer, 1.5-3 parts of vulcanizing agent and 1.5-3 parts of accelerator, wherein the sum of the parts by weight of the natural rubber and the solution-polymerized styrene-butadiene rubber is 100 parts.
3. The rubber compound for elastic joints according to claim 1, wherein the solution-polymerized styrene-butadiene rubber is a solution-polymerized styrene-butadiene rubber having a styrene content of 15% and a vinyl content of 30%.
4. The rubber compound for the elastic node as recited in any one of claims 1 to 3, wherein the reinforcing agent comprises 20 to 30 parts of white carbon black and carbon black.
5. Rubber compound for elastic joints according to claim 4, characterised in that said white carbon black is such that its specific surface area is greater than 110m2White carbon black in a ratio of/g.
6. A rubber compound for elastic joints according to claim 1, characterised in that the vulcanising agents are sulphur and N, N' -m-phenylene bismaleimide and the accelerator is N-tert-butyl-2-benzothiazolesulfenamide in combination with tetrabenzyldithiothiuram.
7. The rubber compound for the elastic joint as claimed in claim 1, characterized by comprising the following components in parts by mass:
75 parts of natural rubber, 25 parts of solution-polymerized styrene-butadiene rubber, 3.5 parts of zinc oxide, 1.5 parts of stearic acid, 30 parts of white carbon black, 30 parts of carbon black, 3 parts of anti-aging agent 4010NA, 2 parts of anti-aging agent RD, 3 parts of paraffin, 3.5 parts of modifier, 12 parts of naphthenic oil, 8 parts of microencapsulation surface-coated and modified high molecular weight crystal form-II ammonium polyphosphate, 1 part of sulfur, 0.5 part of N, N' -m-phenylene bismaleimide, 1 part of accelerator TBZTD and 2 parts of accelerator TBBS.
8. A preparation method of a rubber compound for elastic nodes is characterized by comprising the following steps:
step 1: putting natural rubber and solution polymerized styrene butadiene rubber into an internal mixer, and mixing for 45-50 s;
step 2: putting the active agent, the anti-aging agent RD and paraffin into an internal mixer, and mixing for 30-40 s;
and step 3: putting the modifier, the reinforcing agent and the flame retardant into an internal mixer together, and mixing for 55-65 s;
and 4, step 4: putting the anti-aging agent 4010NA and the plasticizer into an internal mixer, mixing to 143 ℃, and continuously mixing for 75-90 s at the temperature of 143-153 ℃ by using an equipment temperature control module;
and 5: discharging the rubber, discharging the rubber to a sheet discharging machine, performing air cooling to obtain master batch, and standing for more than 2 hours;
step 6: putting the cooled and parked master batch into an internal mixer, and mixing for 35-40 s;
and 7: and (3) putting a vulcanizing agent and an accelerant into an internal mixer, mixing for 40-50 s, lifting and lifting a top plug for 1 time, continuously mixing to 105 ℃, discharging rubber, discharging a piece from a piece discharging machine, and performing air cooling to obtain the fireproof rubber material for the elastic node.
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