CN111440362B - Rubber material of laminated spring and preparation method thereof - Google Patents
Rubber material of laminated spring and preparation method thereof Download PDFInfo
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- CN111440362B CN111440362B CN202010467233.8A CN202010467233A CN111440362B CN 111440362 B CN111440362 B CN 111440362B CN 202010467233 A CN202010467233 A CN 202010467233A CN 111440362 B CN111440362 B CN 111440362B
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 107
- 239000005060 rubber Substances 0.000 title claims abstract description 107
- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims description 11
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 39
- 239000005064 Low cis polybutadiene Substances 0.000 claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 36
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 36
- 229920001194 natural rubber Polymers 0.000 claims abstract description 36
- 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 23
- 239000003063 flame retardant Substances 0.000 claims abstract description 23
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 22
- 239000003607 modifier Substances 0.000 claims abstract description 20
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 20
- 239000004014 plasticizer Substances 0.000 claims abstract description 18
- 239000013543 active substance Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims description 61
- 239000006229 carbon black Substances 0.000 claims description 43
- 238000007599 discharging Methods 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 21
- 239000004594 Masterbatch (MB) Substances 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 2
- -1 tolylene diphenyl phosphate Chemical compound 0.000 claims 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 abstract description 21
- 238000012360 testing method Methods 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- XMNDMAQKWSQVOV-UHFFFAOYSA-N (2-methylphenyl) diphenyl phosphate Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 XMNDMAQKWSQVOV-UHFFFAOYSA-N 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 235000021355 Stearic acid Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 239000008117 stearic acid Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- REQPQFUJGGOFQL-UHFFFAOYSA-N dimethylcarbamothioyl n,n-dimethylcarbamodithioate Chemical compound CN(C)C(=S)SC(=S)N(C)C REQPQFUJGGOFQL-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009661 fatigue test Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- SPAUYKHQVLTCOL-UHFFFAOYSA-N C1(=CC=CC=C1)OP(OC1=CC=CC=C1)(O)=O.C1(=CC=CC=C1)C Chemical compound C1(=CC=CC=C1)OP(OC1=CC=CC=C1)(O)=O.C1(=CC=CC=C1)C SPAUYKHQVLTCOL-UHFFFAOYSA-N 0.000 description 1
- 239000005063 High cis polybutadiene Substances 0.000 description 1
- PUTZDSUOPCPZMG-UHFFFAOYSA-N P(=O)(O)(O)O.C1(=CC=CC=C1)C(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound P(=O)(O)(O)O.C1(=CC=CC=C1)C(C1=CC=CC=C1)C1=CC=CC=C1 PUTZDSUOPCPZMG-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 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
- 230000003287 optical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000036316 preload Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a rubber material of a laminated spring, which comprises the following components in parts by mass: 60-80 parts of natural rubber, 20-40 parts of low cis-polybutadiene rubber, 30-45 parts of reinforcing agent, 5-12 parts of active agent, 2-8 parts of anti-aging agent, 1-3 parts of modifier, 3-10 parts of flame retardant, 3-15 parts of plasticizer, 1-3 parts of vulcanizing agent and 2-5 parts of accelerator; wherein the total of the natural rubber and the low cis-polybutadiene rubber is 100 parts. The mechanical property and the combustion property of the laminated spring rubber material can meet the technical index requirements, so that the technical problem that the rubber material of the laminated spring in the prior art cannot meet the requirements of the combustion property and the mechanical property at the same time is solved, and the rubber material in the prior art cannot be used for rubber elastic elements such as laminated springs of railway vehicles and the like.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a rubber material of a laminated spring and a preparation method thereof.
Background
Modern railway vehicles use a large number of various rubber-elastic elements in the suspension systems, equipment mounting systems, connections, stops, etc. However, the rubber elements belong to flammable or combustible materials, once a fire disaster occurs, the rubber material can be combusted, a large amount of heat and smoke can be emitted, the smoke often has certain toxicity, evacuation and escape of people in the case of the fire disaster of the vehicle are not facilitated, and fire safety hazards in the case of the fire disaster are increased.
Currently, the standard EN45545-2 is used in many countries to regulate the fire performance requirements of materials and components for railway vehicles. The EN45545-2 standard imposes definite requirements on the combustion behaviour of rubber-metal elastic elements used on railway vehicle bogies.
However, the laminated spring or flat rubber pile is an important shock-absorbing elastic element, and is widely applied to high-speed trains such as subway vehicles, urban light rail vehicles and motor train units. However, the combustion performance of the rubber spring manufactured in the prior art does not meet the requirements of the standard EN45545-2, so that the fire safety hazard is serious.
Disclosure of Invention
The invention aims to provide a rubber material of a laminated spring and a preparation method thereof, and aims to solve the technical problem that the rubber material of the laminated spring in the prior art cannot enable the combustion performance and the mechanical performance to simultaneously meet the standard requirements.
In order to realize the purpose, the invention adopts the following technical scheme:
the rubber material of the laminated spring comprises the following components in parts by mass:
60-80 parts of natural rubber, 20-40 parts of low cis-polybutadiene rubber, 30-45 parts of reinforcing agent, 5-12 parts of active agent, 2-8 parts of anti-aging agent, 1-3 parts of modifier, 3-10 parts of flame retardant, 3-15 parts of plasticizer, 1-3 parts of vulcanizing agent and 2-5 parts of accelerator; wherein the total mass part of the natural rubber and the low cis-polybutadiene rubber is 100 parts.
Preferably, the composition comprises the following components in parts by mass: 70 parts of natural rubber, 30 parts of low cis-polybutadiene rubber, 30-45 parts of reinforcing agent, 5-12 parts of activator, 2-8 parts of anti-aging agent, 1-3 parts of modifier, 3-10 parts of flame retardant, 3-15 parts of plasticizer, 1-3 parts of vulcanizing agent and 2-5 parts of accelerator.
Preferably, the reinforcing agent comprises 8-28 parts of carbon black and 10-30 parts of white carbon black.
Preferably, the low-cis polybutadiene rubber preferably has a cis-1, 4-butadiene content of 35% and a vinyl content of 10%.
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 modifier is a silane coupling agent, and the mass of the silane coupling agent is 10% of the mass of the white carbon black.
Preferably, the plasticizer comprises diphenyl cresyl phosphate and naphthenic oil, and the mass ratio of the diphenyl cresyl phosphate to the naphthenic oil is 1: 1.
Preferably, the vulcanizing agent is sulfur, and the accelerator is a combination of tetramethyl thiuram and N-cyclohexyl-2-benzothiazole sulfonamide.
A preparation method of a rubber compound of a laminated spring comprises the following steps:
s1: putting natural rubber and low cis-polybutadiene rubber into an internal mixer, and mixing for 30-45 s;
s2: putting the active agent and the anti-aging agent into an internal mixer, and mixing for 30-40 s;
s3: simultaneously putting the modifier, the reinforcing agent and the flame retardant into an internal mixer, and mixing for 45-60 s;
s4: putting the plasticizer into an internal mixer, mixing to 143 ℃, and continuously mixing for 60-70s at the temperature of 143-153 ℃ by using an equipment temperature control module;
s5: 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;
s6: putting the cooled and parked master batch into an internal mixer, and mixing for 30-40 s;
s7: and (3) putting a vulcanizing agent and an accelerant into an internal mixer, mixing for 30-40s, lifting and lifting a top plug for 1 time, mixing to 105 ℃, discharging rubber, discharging the rubber from a sheet discharging machine, and cooling by air cooling to obtain the rubber material of the laminated spring.
Compared with the prior art, the invention has the advantages and beneficial effects that:
the rubber compound suitable for the laminated spring is prepared by mixing natural rubber and low cis-polybutadiene rubber and reasonably optimizing and matching the reinforcing agent and the flame retardant, and the prepared laminated spring 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 properties also meet the requirements of the standards of TB/T2841-. The technical problem that in the prior art, the rubber material of the laminated spring cannot meet the requirements of combustion performance and mechanical performance at the same time is solved, so that the rubber material in the prior art cannot be used for rubber elastic elements such as laminated springs of railway vehicles and the like.
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 laminated spring is prepared by mixing natural rubber and low cis-polybutadiene rubber and reasonably optimizing and matching the reinforcing agent and the flame retardant, and the prepared laminated spring 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 properties also meet the requirements of the standards of TB/T2841-. The technical problem that in the prior art, the rubber material of the laminated spring cannot meet the requirements of combustion performance and mechanical performance at the same time is solved, so that the rubber material in the prior art cannot be used for rubber elastic elements such as laminated springs of railway vehicles.
Specifically, the coating comprises the following components in parts by mass:
60-80 parts of natural rubber, 20-40 parts of low cis-polybutadiene rubber, 30-45 parts of reinforcing agent, 5-12 parts of active agent, 2-8 parts of anti-aging agent, 1-3 parts of modifier, 3-10 parts of flame retardant, 3-15 parts of plasticizer, 1-3 parts of vulcanizing agent and 2-5 parts of accelerator; wherein the total of the natural rubber and the low cis-polybutadiene rubber is 100 parts.
In a preferred embodiment, the natural rubber is 70 parts and the low cis polybutadiene rubber is 30 parts.
Further, the natural rubber can be selected from constant-viscosity rubber or smoked sheet rubber, wherein the natural rubber is preferably constant-viscosity rubber CV 60; the cis-1, 4-butadiene content of the low cis-polybutadiene rubber is 30-40%, and the vinyl content is 8-10%.
In a preferred embodiment, the low cis polybutadiene rubber is further preferably 35% cis 1, 4-butadiene and 10% vinyl.
Furthermore, the end group of the low cis-polybutadiene rubber is functionally modified, and the end group of the low cis-polybutadiene rubber can improve the dispersibility of the carbon black and the interface bonding capability between the rubber and the carbon black after the functional modification. Specifically, the low cis-polybutadiene rubber has better rebound resilience, low temperature performance, heat resistance and aging resistance, and is good in compatibility with natural rubber. The low cis-polybutadiene rubber is used together to replace partial natural rubber, and can achieve good blending modification effect on the natural rubber. The low cis-polybutadiene rubber has high thermal decomposition temperature and better heat resistance than natural rubber. The low cis-polybutadiene rubber reduces the proportion of natural rubber in rubber materials and improves the heat resistance and the thermal decomposition temperature of the rubber materials. And the carbon layer can be changed from a dispersed state to a continuous compact state after the rubber material is combusted, the continuous compact carbon layer can play a better heat insulation protection role on the unburned polymer at the lower layer, and the combustion performance of the rubber is greatly improved.
In a preferred embodiment, the white carbon black preferably has a specific surface area of more than 110m2White carbon black in a ratio of/g.
In a preferred embodiment, the modifier is a silane coupling agent, and the dosage of the silane coupling agent is 10% of the dosage of the white carbon black.
In a preferred embodiment, the reinforcing agent includes 8 to 28 parts of carbon black and 10 to 30 parts of white carbon black. 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.
In a preferred embodiment, the plasticizer is a mixture of cresyldiphenyl phosphate and naphthenic oil; the mass ratio of the toluene diphenyl phosphate to the naphthenic oil is 1: 1. Naphthenic oil is a common plasticizer for natural rubber, but belongs to small molecule combustible substances; the diphenyl cresyl phosphate has a certain flame-retardant effect, and rubber sizing materials can promote charring and improve the combustion performance of the rubber sizing materials when being combusted, but the diphenyl cresyl phosphate belongs to polar substances and has poor compatibility with natural rubber and low cis-polybutadiene rubber, so the dosage of the diphenyl cresyl phosphate needs to be strictly controlled. Therefore, the diphenyl cresyl phosphate and the naphthenic oil are matched for use, the expected plasticizing effect is achieved, and the combustibility is also considered, so that the rubber compound meeting the mechanical property and the combustion property simultaneously can be obtained through reasonable matching of the formulas, and the rubber compound of the laminated spring with the fireproof function can be obtained.
In order to better explain a rubber compound for a laminated spring and a method for preparing the same, a detailed description will be given below with reference to comparative examples and examples.
Comparative example
The rubber compound of the laminated spring comprises the following components in parts by mass:
70 parts of natural rubber, 30 parts of high cis-polybutadiene rubber, 5 parts of zinc oxide, 2 parts of stearic acid, 1.8 parts of sulfur, 0.4 part of accelerator MBTS, 1.5 parts of accelerator CBS, 38 parts of carbon black, 4010NA2 parts of anti-aging agent RD, 1.5 parts of paraffin and 8 parts of naphthenic oil.
The preparation method comprises the following specific steps:
manufacturing equipment and 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 35-45r/min, and the rotor speed of the internal mixer in the following steps 6-7 is 15-20 r/min.
Step 1: putting natural rubber and low cis-polybutadiene rubber into an internal mixer, and mixing for 30-45 s;
step 2: putting the active agent and the anti-aging agent 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 45-60 s;
and 4, step 4: putting the plasticizer into an internal mixer, mixing to 143 ℃, and continuously mixing for 60-70s 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 30-40 s;
and 7: and (3) putting a vulcanizing agent and an accelerant into an internal mixer, mixing for 30-40s, lifting and lifting a top plug for 1 time, mixing to 105 ℃, discharging rubber, discharging the rubber from a sheet discharging machine, and cooling by air cooling to obtain the rubber material of the laminated spring.
Example 1
The rubber compound of the laminated spring comprises the following components in parts by mass:
80 parts of natural rubber, 20 parts of low cis-polybutadiene rubber, 5 parts of zinc oxide, 2 parts of stearic acid, 1.6 parts of sulfur, 0.5 part of accelerator TMTM, 1.5 parts of accelerator CBS, 30 parts of white carbon black, 15 parts of carbon black, 4010NA2 parts of anti-aging agent, 1 part of anti-aging agent RD, 1 part of paraffin, 3 parts of modifier, 7 parts of diphenyl toluate phosphate, 7 parts of naphthenic oil and 3 parts of high molecular weight crystal form-II ammonium polyphosphate.
The preparation method comprises the following specific steps:
manufacturing equipment and 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 35-45r/min, and the rotor speed of the internal mixer in the following steps 6-7 is 15-20 r/min.
Step 1: putting natural rubber and low cis-polybutadiene rubber into an internal mixer, and mixing for 30-45 s;
step 2: putting the active agent and the anti-aging agent 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 45-60 s;
and 4, step 4: putting the plasticizer into an internal mixer, mixing to 143 ℃, and continuously mixing for 60-70s 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 30-40 s;
and 7: and (3) putting a vulcanizing agent and an accelerant into an internal mixer, mixing for 30-40s, lifting and lifting a top plug for 1 time, mixing to 105 ℃, discharging rubber, discharging the rubber from a sheet discharging machine, and cooling by air cooling to obtain the rubber material of the laminated spring.
Example 2
The rubber compound of the laminated spring comprises the following components in parts by mass:
70 parts of natural rubber, 30 parts of low cis-polybutadiene rubber, 5 parts of zinc oxide, 2 parts of stearic acid, 1.6 parts of sulfur, 1.5 parts of accelerator TMTM, 3.5 parts of accelerator CBS, 20 parts of white carbon black, 18 parts of carbon black, 3 parts of anti-aging agent 4010NA, 3 parts of anti-aging agent RD, 1 part of paraffin, 2 parts of modifier, 4 parts of diphenyl toluate phosphate, 4 parts of naphthenic oil and 5 parts of high molecular weight crystal form-II ammonium polyphosphate.
The preparation method comprises the following specific steps:
manufacturing equipment and 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 35-45r/min, and the rotor speed of the internal mixer in the following steps 6-7 is 15-20 r/min.
Step 1: putting natural rubber and low cis-polybutadiene rubber into an internal mixer, and mixing for 30-45 s;
step 2: putting the active agent and the anti-aging agent 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 45-60 s;
and 4, step 4: putting the plasticizer into an internal mixer, mixing to 143 ℃, and continuously mixing for 60-70s 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 30-40 s;
and 7: and (3) putting a vulcanizing agent and an accelerant into an internal mixer, mixing for 30-40s, lifting and lifting a top plug for 1 time, mixing to 105 ℃, discharging rubber, discharging the rubber from a sheet discharging machine, and cooling by air cooling to obtain the rubber material of the laminated spring.
Example 3
The rubber compound of the laminated spring comprises the following components in parts by mass:
60 parts of natural rubber, 40 parts of low cis-polybutadiene rubber, 5 parts of zinc oxide, 2 parts of stearic acid, 1.6 parts of sulfur, 0.5 part of accelerator TMTM, 1.5 parts of accelerator CBS, 10 parts of white carbon black, 20 parts of carbon black, 2 parts of anti-aging agent 4010NA, 0.5 part of anti-aging agent RD, 0.5 part of paraffin, 1 part of modifier, 1.5 parts of diphenyl cresyl phosphate, 1.5 parts of naphthenic oil and 8 parts of high molecular weight crystal form-II ammonium polyphosphate.
The preparation method comprises the following specific steps:
manufacturing equipment and 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 35-45r/min, and the rotor speed of the internal mixer in the following steps 6-7 is 15-20 r/min.
Step 1: putting natural rubber and low cis-polybutadiene rubber into an internal mixer, and mixing for 30-45 s;
step 2: putting the active agent and the anti-aging agent 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 45-60 s;
and 4, step 4: putting the plasticizer into an internal mixer, mixing to 143 ℃, and continuously mixing for 60-70s 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 30-40 s;
and 7: and (3) putting a vulcanizing agent and an accelerant into an internal mixer, mixing for 30-40s, lifting and lifting a top plug for 1 time, mixing to 105 ℃, discharging rubber, discharging the rubber from a sheet discharging machine, and cooling by air cooling to obtain the rubber material of the laminated spring.
Example 4
The rubber compound of the laminated spring comprises the following components in parts by mass:
55 parts of natural rubber, 45 parts of low cis-polybutadiene rubber, 5 parts of zinc oxide, 2 parts of stearic acid, 1.6 parts of sulfur, 1.5 parts of an accelerator TMTM, 3.5 parts of an accelerator CBS, 20 parts of white carbon black, 18 parts of carbon black, 3 parts of an anti-aging agent 4010NA, 3 parts of an anti-aging agent RD, 1 part of paraffin, 2 parts of a modifier, 4 parts of diphenyl toluate phosphate, 4 parts of naphthenic oil and 3 parts of high molecular weight crystal form-II ammonium polyphosphate.
The preparation method comprises the following specific steps:
manufacturing equipment and 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 35-45r/min, and the rotor speed of the internal mixer in the following steps 6-7 is 15-20 r/min.
Step 1: putting natural rubber and low cis-polybutadiene rubber into an internal mixer, and mixing for 30-45 s;
step 2: putting the active agent and the anti-aging agent 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 45-60 s;
and 4, step 4: putting the plasticizer into an internal mixer, mixing to 143 ℃, and continuously mixing for 60-70s 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 30-40 s;
and 7: and (3) putting a vulcanizing agent and an accelerant into an internal mixer, mixing for 30-40s, lifting and lifting a top plug for 1 time, mixing to 105 ℃, discharging rubber, discharging the rubber from a sheet discharging machine, and cooling by air cooling to obtain the rubber material of the laminated spring.
The test standards and methods of the rubber material and the product of the laminated spring 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 CITGAccording to EN 45545-2:201 respectively3, ISO5660-1, ISO5659-2, with an irradiance of 25kW/m2。
3. And (3) testing the mechanical properties of the product:
a) static vertical stiffness and constant load high test:
applying a vertical load to the laminated spring at the ambient temperature of 23 ℃, repeating for 3 cycles, wherein the loading range is as follows: 0 kN-169 kN-0 kN at the speed of 60mm/min, recording a curve of the 3 rd cycle, and finding a point with the load of 110kN at the rising stage of the curve, thereby calculating the static vertical stiffness of the laminated spring when the load is 110 kN; and immediately performing a compression high test after the vertical rigidity is finished, wherein the speed is 50mm/min, the vertical loading is 0-169 kN, then the load is unloaded to 110kN, the load is kept for 10s, and the constant load of the product is measured to be high.
b) High and low temperature tests: respectively placing the product at the constant temperature of minus 40 ℃ and 50 ℃ for 24 hours, and measuring the static vertical rigidity and the constant load of the product at each temperature according to the procedure in the step a).
c) And (3) fatigue test: at the ambient temperature of 23 ℃, the vertical preload is 135kN, the dynamic vertical load is +/-40 kN, the circulation is 200 ten thousand times under the condition of the frequency of 1Hz, the freedom of the product after the fatigue test is high, and the static vertical rigidity and the fixed load after the product is tested to be fatigue are high according to the program in the a).
d) Thermal aging test: the product is placed in an environment box at 70 ℃ for 14 days, taken out and placed in an environment at 23 ℃ for 24 hours, and then the static vertical rigidity of the product is tested according to the procedure in the step a).
e) Static creep test: applying a vertical load of 0-169 kN to the laminated spring at the ambient temperature of 23 ℃, wherein the speed is 60mm/min, repeating 3 pre-cycles, loading the vertical load to 110kN at the 4 th cycle, keeping the load unchanged, starting to record the process of the height of the laminated spring along with time by taking the vertical load as 0 point at the moment, keeping the load for 7 days, measuring the creep amount and presuming the creep amount in the life period; and the static vertical stiffness of the product after creep is detected.
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 laminated spring product Performance comparative data
It can be seen from tables 1 and 3 that the mechanical properties, product properties and mechanical properties in the prior art of the rubber compound of the laminated spring provided by the invention can all meet the technical requirements, and it can be seen from table 1 that when the total amount of raw rubber is 100 parts, wherein the natural rubber content is 60-80 parts, and the amount of the low cis-polybutadiene rubber is 20-40 parts, the prepared rubber compound of the laminated spring meets the requirements of the mechanical properties of the rubber compound; when the dosage of the low cis-polybutadiene rubber exceeds 40 parts, the mechanical strength of the rubber material is low, and the technical requirements cannot be met. Further, it can be seen from table 2 that the comparative example cannot satisfy the burning performance of the rubber material, however, the invention combines natural rubber and low-cis polybutadiene rubber, uses ammonium polyphosphate as a flame retardant, uses diphenyl toluene phosphate with flame retardant effect as a plasticizer, and uses carbon black and white carbon black as a reinforcing agent, so that the rubber material of the laminated spring in the invention can satisfy the requirements of burning performance EN 45545-2R 9 HL2 on the premise of satisfying the technical requirements of mechanical performance by reasonably optimizing and matching the components, thereby solving the problem that the burning performance of the rubber material of the laminated spring in the prior art cannot satisfy the requirements of EN 45545-2R 9 HL 2.
Example 5
In this embodiment, based on example 1, the contents of carbon black and white carbon black of the reinforcing agent in the components are 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 shows the results of testing the properties of the rubber mixtures at different amounts of carbon black and white carbon black
In Table 4, 1# -5# is 5 different test formulas, in which only the blending ratio of carbon black and silica is changed, and other components are the same as those in example 1. As can be seen from Table 4, on the premise of keeping consistent hardness of the rubber compound, as the amount of the white carbon black is increased, the compression set of the rubber compound is increased, the stress at definite elongation is reduced, and other mechanical properties are not changed much, however, MARHE and D in the combustion performance indexesS maxThe improvement is gradual. For rubber elastic elements such as laminated springs, the smaller the compression set, the better, and thus the smaller the amount of white carbon used, the better, in the case where the combustion performance can meet the specifications. And it can be seen in table 4 that when the amount of white carbon black is 10-30 parts and the amount of carbon black is 8-28 parts, the performance of the rubber compound meets the requirements of various technical indexes.
Claims (10)
1. The rubber material of the laminated spring is characterized by comprising the following components in parts by mass:
60-80 parts of natural rubber, 20-40 parts of low cis-polybutadiene rubber, 30-45 parts of reinforcing agent, 5-12 parts of active agent, 2-8 parts of anti-aging agent, 1-3 parts of modifier, 3-10 parts of flame retardant, 3-15 parts of plasticizer, 1-3 parts of vulcanizing agent and 2-5 parts of accelerator; wherein the total mass part of the natural rubber and the low cis-polybutadiene rubber is 100 parts, and the flame retardant is ammonium polyphosphate modified by microencapsulation surface coating.
2. The rubber compound of the laminated spring according to claim 1, characterized by comprising the following components in parts by mass: 70 parts of natural rubber, 30 parts of low cis-polybutadiene rubber, 30-45 parts of reinforcing agent, 5-12 parts of activator, 2-8 parts of anti-aging agent, 1-3 parts of modifier, 3-10 parts of flame retardant, 3-15 parts of plasticizer, 1-3 parts of vulcanizing agent and 2-5 parts of accelerator.
3. The rubber compound of the laminated spring according to claim 1 or 2, wherein the reinforcing agent comprises 8-28 parts of carbon black and 10-30 parts of white carbon black.
4. Rubber compound for laminated springs according to claim 1, characterized in that the low-cis polybutadiene rubber has a cis 1, 4-butadiene content of preferably 35% and a vinyl content of preferably 10%.
5. Rubber compound for laminated springs according to claim 3, characterised in that the white carbon black is preferably selected with a specific surface area of more than 110m2White carbon black in a ratio of/g.
6. The rubber compound for laminated springs according to claim 5, characterized in that the flame retardant is preferably a microencapsulated surface-coating-modified high molecular weight form II ammonium polyphosphate.
7. The rubber compound for laminated springs according to claim 3, wherein the modifier is a silane coupling agent, and the mass of the silane coupling agent is 10% of the mass of the white carbon black.
8. The rubber compound for laminated springs according to claim 1, wherein the plasticizer comprises tolylene diphenyl phosphate and naphthenic oil, and the mass ratio of tolylene diphenyl phosphate to naphthenic oil is 1: 1.
9. Rubber compound for laminated springs according to claim 1, characterized in that the vulcanizing agent is preferably sulfur and the accelerator is preferably a combination of tetramethyl monothiothiuram and N-cyclohexyl-2-benzothiazolesulfenamide.
10. The preparation method of the rubber compound of the laminated spring is characterized by comprising the following steps of:
s1: putting natural rubber and low cis-polybutadiene rubber into an internal mixer, and mixing for 30-45 s;
s2: putting the active agent and the anti-aging agent into an internal mixer, and mixing for 30-40 s;
s3: simultaneously putting the modifier, the reinforcing agent and the flame retardant into an internal mixer, and mixing for 45-60 s;
s4: putting the plasticizer into an internal mixer, mixing to 143 ℃, and continuously mixing for 60-70s at the temperature of 143-153 ℃ by using an equipment temperature control module;
s5: 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;
s6: putting the cooled and parked master batch into an internal mixer, and mixing for 30-40 s;
s7: and (3) putting a vulcanizing agent and an accelerant into an internal mixer, mixing for 30-40s, lifting and lifting a top plug for 1 time, mixing to 105 ℃, discharging rubber, discharging the rubber from a sheet discharging machine, and cooling by air cooling to obtain the rubber material of the laminated spring.
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