CN115521511B - Rubber composition and preparation method and application thereof - Google Patents
Rubber composition and preparation method and application thereof Download PDFInfo
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- CN115521511B CN115521511B CN202211133008.6A CN202211133008A CN115521511B CN 115521511 B CN115521511 B CN 115521511B CN 202211133008 A CN202211133008 A CN 202211133008A CN 115521511 B CN115521511 B CN 115521511B
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 111
- 239000005060 rubber Substances 0.000 title claims abstract description 111
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 27
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 27
- 229920001194 natural rubber Polymers 0.000 claims abstract description 27
- 238000004073 vulcanization Methods 0.000 claims abstract description 23
- 239000006229 carbon black Substances 0.000 claims abstract description 22
- 239000013543 active substance Substances 0.000 claims abstract description 17
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000012188 paraffin wax Substances 0.000 claims abstract description 14
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 11
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 8
- 241000208125 Nicotiana Species 0.000 claims abstract description 7
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims abstract description 7
- 238000010008 shearing Methods 0.000 claims abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 25
- 229910052717 sulfur Inorganic materials 0.000 claims description 23
- 239000011593 sulfur Substances 0.000 claims description 23
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 229920002857 polybutadiene Polymers 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 2
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 150000004989 p-phenylenediamines Chemical class 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 claims description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 2
- 229960002447 thiram Drugs 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- 238000001914 filtration Methods 0.000 abstract description 5
- 238000010998 test method Methods 0.000 description 18
- 238000013016 damping Methods 0.000 description 9
- 239000005062 Polybutadiene Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 241000063973 Mattia Species 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- HLBZWYXLQJQBKU-UHFFFAOYSA-N 4-(morpholin-4-yldisulfanyl)morpholine Chemical compound C1COCCN1SSN1CCOCC1 HLBZWYXLQJQBKU-UHFFFAOYSA-N 0.000 description 1
- 102100034088 40S ribosomal protein S4, X isoform Human genes 0.000 description 1
- 101000732165 Homo sapiens 40S ribosomal protein S4, X isoform Proteins 0.000 description 1
- 101100478969 Oryza sativa subsp. japonica SUS2 gene Proteins 0.000 description 1
- 101100004663 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) BRR2 gene Proteins 0.000 description 1
- 101100504519 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) GLE1 gene Proteins 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60G—VEHICLE SUSPENSION ARRANGEMENTS
- B60G7/00—Pivoted suspension arms; Accessories thereof
- B60G7/04—Buffer means for limiting movement of arms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60G—VEHICLE SUSPENSION ARRANGEMENTS
- B60G2206/00—Indexing codes related to the manufacturing of suspensions: constructional features, the materials used, procedures or tools
- B60G2206/01—Constructional features of suspension elements, e.g. arms, dampers, springs
- B60G2206/70—Materials used in suspensions
- B60G2206/71—Light weight materials
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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)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a rubber composition and a preparation method and application thereof, wherein the rubber composition comprises a rubber matrix, reinforcing filler, an anti-aging agent, paraffin, an active agent and a vulcanization system, the rubber matrix comprises natural rubber and cis-1, 4-polybutadiene rubber, the natural rubber is tobacco flake rubber, and the weight average molecular weight of the cis-1, 4-polybutadiene rubber is 200000-400000; the reinforcing filler is carbon black, the specific surface area is 20-30m 2/g, the oil absorption value is 110-140mL/100g, and the screen residue is less than or equal to 100ppm; preparation: the rubber composition with excellent vibration filtering performance and longer service life is obtained by putting other components except a vulcanization system into an internal mixer for shearing and mixing to obtain master batch, mixing the master batch with the vulcanization system, and vulcanizing.
Description
Technical Field
The invention relates to the field of automotive suspension bushings, in particular to a rubber composition with low dynamic hardening performance, and specifically relates to a rubber composition, and a preparation method and application thereof.
Background
In the continuous development process of the automobile industry, the teaching of a chassis suspension is always one of the most central problems. How to teach the safety, comfort and operability of the chassis suspension according to the product positioning of the automobile is a continuous balancing and adjusting process. Among these, rubber, which is the most common vibration-absorbing material, has been widely used in the automotive industry for a long time, because of its special hysteresis damping characteristics, it can perform vibration isolation and improve comfort. However, in actual use, particularly in the high-speed running process of an automobile, the vibration filtering performance of a common rubber damping part is obviously reduced under the high-frequency vibration condition, and the service life of the rubber damping part is obviously influenced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an improved rubber composition with excellent vibration filtering performance and longer service life.
The invention also provides a preparation method of the rubber composition.
The invention also provides application of the rubber composition in preparation of an automobile suspension bushing.
In order to achieve the above purpose, the invention adopts a technical scheme that: a rubber composition comprising the following components: rubber matrix, reinforcing filler, anti-aging agent, paraffin, active agent and vulcanization system, wherein: the rubber matrix comprises natural rubber and cis-1, 4-polybutadiene rubber, the natural rubber is tobacco flake rubber, the weight average molecular weight of the cis-1, 4-polybutadiene rubber is 200000-400000, and the feeding mass ratio of the natural rubber to the cis-polybutadiene rubber is 1:0.10-0.45;
The reinforcing filler is carbon black, the specific surface area of the carbon black is 20-30m 2/g, the oil absorption value is 110-140mL/100g, and the screen residue is less than or equal to 100ppm;
the mass ratio of the carbon black to the rubber matrix is 0.2-0.7:1.
According to some preferred aspects of the invention, the carbon black has a specific surface area of 25-30m 2/g, an oil absorption value of 115-130mL/100g, and a screen residue of 50ppm or less.
In the present invention, the specific surface area is measured by ASTM D6556, the oil absorption value (OAN) is measured by ASTM D2414, and the screen residue is measured by ASTM D1514.
According to a particular aspect of the invention, the carbon black is an Euro-engineered carbon groupHS 25。
In some preferred embodiments of the invention, the tobacco flake gum has a molecular weight of 1.5X10 6-2.0×106.
In some preferred embodiments of the invention, the natural rubber is grade 1 tobacco flake rubber (RSS 1), commercially available.
In some preferred embodiments of the present invention, the cis-1, 4-polybutadiene rubber is rubber butadiene rubber BR9000, commercially available.
According to some preferred aspects of the present invention, the vulcanization system comprises sulfur, an accelerator and a sulfur carrier, wherein the sulfur, the accelerator and the sulfur carrier are added in a mass ratio of 1:0.25-2.0:0.12-0.80.
According to some preferred aspects of the present invention, the rubber composition comprises, in parts by weight, 70 to 90 parts of natural rubber, 10 to 30 parts of cis-1, 4-polybutadiene rubber, 20 to 70 parts of carbon black, 2.0 to 5.0 parts of an anti-aging agent, 3.0 to 5.0 parts of paraffin wax, 5.0 to 9.0 parts of an active agent, 2.0 to 4.0 parts of sulfur, 1.0 to 4.0 parts of an accelerator, and 0.5 to 1.5 parts of a sulfur carrier.
Further, in the rubber composition, 70-90 parts by weight of natural rubber, 10-30 parts by weight of cis-1, 4-polybutadiene rubber, 20-60 parts by weight of carbon black, 2.0-5.0 parts by weight of an anti-aging agent, 3.0-5.0 parts by weight of paraffin wax, 5.0-9.0 parts by weight of an active agent, 2.0-4.0 parts by weight of sulfur, 1.0-4.0 parts by weight of an accelerator and 0.5-1.5 parts by weight of a sulfur carrier.
Further, the rubber composition comprises, by weight, 70-85 parts of natural rubber, 15-30 parts of cis-1, 4-polybutadiene rubber, 25-45 parts of carbon black, 3.0-5.0 parts of an anti-aging agent, 3.0-4.0 parts of paraffin wax, 6.0-8.0 parts of an active agent, 2.0-4.0 parts of sulfur, 1.5-3.5 parts of an accelerator and 0.5-1.0 parts of a sulfur carrier.
According to some preferred aspects of the invention, the mass ratio of the carbon black to the rubber matrix is 0.2-0.5:1.
According to some preferred aspects of the present invention, the antioxidant is one or a combination of more selected from ketoamine antioxidants, diphenylamine derivative antioxidants, p-phenylenediamine derivative antioxidants, environmentally friendly hindered phenol antioxidants, hindered diphenol antioxidants.
According to some preferred aspects of the invention, the active agent is an inorganic active agent comprising zinc oxide and/or an organic active agent which is stearic acid.
According to some preferred aspects of the invention, the paraffin wax is microcrystalline paraffin wax.
In some preferred embodiments of the invention, the microcrystalline wax has a molecular weight of 490 to 800 and a freezing point of 50 to 70 ℃.
According to some preferred aspects of the invention, the sulfur is insoluble sulfur.
According to some preferred aspects of the invention, the accelerator is one or more selected from thiazole-based accelerators, sulfenamide-based accelerators, thiuram-based accelerators, guanidine-based accelerators.
In some embodiments of the invention, the accelerator is a combination of one or more selected from the group consisting of N-tert-butyl-2-benzothiazole sulfenamide, 2' -dithiodibenzothiazyl and diphenyl guanidine.
According to a specific aspect of the invention, the accelerator consists of N-tertiary butyl-2-benzothiazole sulfenamide, 2 '-dithiodibenzothiazyl and diphenylguanidine, and the feeding mass ratio of the N-tertiary butyl-2-benzothiazole sulfenamide, the 2,2' -dithiodibenzothiazyl and the diphenylguanidine is 1:0.8-1.2:0.1-0.3.
According to some preferred aspects of the invention, the sulphur carrier is 1, 1-dithiobiscaprolactam (CLD) and/or 4,4' -dithiodimorpholine (DTDM).
The invention provides another technical scheme that: the preparation method of the rubber composition comprises the following steps:
Adding other components except the vulcanization system into an internal mixer for shearing and mixing, wherein the mixing temperature is not more than 145 ℃, discharging tablets, cooling and standing to obtain master batch;
mixing the master batch and the vulcanization system, carrying out mixing, wherein the mixing temperature is not higher than 100 ℃, discharging the sheet to obtain a mixed rubber mixture, standing, and carrying out vulcanization to obtain the rubber composition.
According to some preferred aspects of the invention, the parking time before obtaining the masterbatch is 20-30 hours.
According to some preferred aspects of the invention, the parking time before the vulcanization is carried out is from 5 to 20 hours.
According to some preferred aspects of the invention, the vulcanization is carried out at 155-165 ℃.
According to some preferred aspects of the invention, the vulcanization time of the vulcanization is from 5 to 15 minutes.
The invention provides another technical scheme that: the application of the rubber composition in preparing the automobile suspension bushing.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
Through a large number of experimental study analysis, the natural rubber with higher molecular weight and cis-1, 4-polybutadiene rubber with specific molecular weight are used together, and under the synergistic effect of proper carbon black serving as a reinforcing material, the friction heat generation in the rubber can be reduced, the good physical and mechanical properties and the dynamic fatigue property are ensured, the dynamic hardening effect can be weakened, namely, a small hysteresis loss angle is brought, and the vibration filtering performance under dynamic high frequency is improved. In summary, the invention can obviously weaken the dynamic hardening effect, improve the dynamic fatigue performance and bring longer service life.
Detailed Description
At present, the general automobile damping rubber is mainly natural rubber, so that excellent physical and mechanical properties and certain damping and damping characteristics can be brought, but in actual use, particularly in the high-speed running process of an automobile, the vibration filtering performance of the general rubber damping member is obviously reduced, and the service life is obviously shortened when the high-speed running is found. Based on the above-mentioned problems of the prior art, the inventor considers, in combination with practical and theoretical research analysis, that on one hand, due to the hysteresis damping performance of natural rubber, it shows the disadvantage of dynamic hardening (stiffness (dynamic stiffness) is significantly affected by an applied frequency under dynamic conditions and increases linearly with increasing frequency), which is disadvantageous for vibration isolation at high frequencies, namely, the disadvantage of dynamic hardening of rubber, which is basically due to hysteresis loss of rubber as a polymer material due to viscoelasticity, under dynamic conditions, particularly at high frequencies, and this hysteresis loss is shown by: when the external force acts, the deformation of the rubber is delayed behind the change of the external force, a certain phase angle (loss angle) is delayed, and the larger the hysteresis loss angle is, the more obvious the influence of frequency is, namely, under the high-frequency external force, the rubber can not absorb the deformation and energy caused by the external force through chain segment movement, so that the rubber is similar to lose elasticity in appearance, and the dynamic stiffness is suddenly improved; on the other hand, under the dynamic condition, the friction heat generation in the rubber is high, so that the dynamic fatigue performance of the rubber is poor, and the service life of the product is further influenced.
Further, the present invention innovatively provides a rubber composition having excellent low dynamic hardening properties and good dynamic fatigue durability.
The inventive concept of the rubber composition is mainly as follows: firstly, natural rubber with higher molecular weight is used, meanwhile, partial butadiene rubber is used, the molecular chain segment has good flexibility, and the conformation of the natural rubber is easy to change, so that better elasticity, smaller hysteresis loss and higher mechanical strength are brought, the advantages of the natural rubber and the butadiene rubber are complementary and mutually cooperate, excellent elasticity and low dynamic hardening are brought, good physical and mechanical properties are ensured, and the durable service life of a damping product is ensured; secondly, in the practical process, the more the carbon black is used as a reinforcing material, the better the physical and mechanical properties of the rubber are, but the higher hysteresis effect is generated due to the friction between a rubber molecular chain and filler ions, so that the dynamic hardening effect is obvious.
Based on this, the present invention provides a rubber composition which can solve the above-mentioned problems of the prior art, the rubber composition comprising the following components: the rubber matrix, reinforcing filler, anti-aging agent, paraffin, active agent and vulcanization system, wherein the resin matrix comprises natural rubber and cis-1, 4-polybutadiene rubber, the natural rubber is tobacco flake rubber, the weight average molecular weight of the cis-1, 4-polybutadiene rubber is 200000-400000, and the feeding mass ratio of the natural rubber to the butadiene rubber is 1:0.10-0.45; the reinforcing filler is carbon black, the specific surface area of the carbon black is 20-30m 2/g, the oil absorption value is 110-140mL/100g, and the screen residue is less than or equal to 100ppm; the mass ratio of the carbon black to the rubber matrix is 0.2-0.7:1.
The above-described aspects are further described below in conjunction with specific embodiments; it should be understood that these embodiments are provided to illustrate the basic principles, main features and advantages of the present invention, and that the present invention is not limited by the scope of the following embodiments; the implementation conditions employed in the examples may be further adjusted according to specific requirements, and the implementation conditions not specified are generally those in routine experiments.
All starting materials are commercially available or prepared by methods conventional in the art, not specifically described in the examples below.
The natural rubber adopts natural rubber first-grade tobacco flake rubber (RSS 1) purchased from Vietnam; butadiene Rubber (BR) is BR9000, a Qilu petrochemical product; microcrystalline paraffin was purchased from Rhine chemistry654; Carbon black is/>HS 25, available from Euro-Euro (specific surface area about 28m 2/g, oil absorption value about 123mL/100g, screen residue less than or equal to 50 ppm); the anti-aging agent is 4010NA anti-aging agent, purchased from Rhine chemistry; insoluble sulphur, purchased from rhena chemistry.
Example 1
The example provides a rubber composition and a preparation method thereof, wherein the rubber composition comprises the following components in mass percent:
The preparation method of the rubber composition comprises the following steps:
1. All raw materials except the vulcanization system are put into an internal mixer for shearing and mixing, the mixing temperature is not more than 145 ℃, and the masterbatch is obtained after sheet discharging, cooling and standing for 24 hours;
2. And (3) putting the master batch and the vulcanization system into an internal mixer for mixing, wherein the mixing temperature is not more than 100 ℃. And (5) discharging the sheet to obtain a rubber compound mixture, and standing for more than 12 hours. And vulcanizing at 160 ℃ for 8min to obtain the rubber composition.
The rubber composition of the example is tested according to a GB/T528 test method, the tensile strength is 24.5MPa, the elongation at break is 519.8%, the hysteresis loss angle is 1.36 degrees (the dynamic hardening effect (weak/strong) of the rubber is represented by an Instron material dynamic stiffness tester, the smaller the hysteresis loss angle is, the weaker the dynamic hardening effect is, and the De mattia endurance fatigue times are more than 2300000 times according to a GB/T13934 test method; the resilience was 82% as measured according to the GB/T1681 test method. The tensile strength after heat aging at 70 ℃/70h according to GB/T3512 is 23.2MPa, the elongation at break is 474%, and the hardness is changed by +2ShA.
Example 2
The example provides a rubber composition and a preparation method thereof, wherein the rubber composition comprises the following components in mass percent:
The preparation method of this example 2 is the same as that of example 1.
The rubber composition of the embodiment is tested according to a GB/T528 test method, the tensile strength is 25.7MPa, the elongation at break is 531.8%, the hysteresis loss angle is 1.89 degrees by using an Instron material dynamic stiffness tester, and the rubber composition is tested according to a GB/T13934 test method, wherein the De mattia endurance fatigue times are more than 2100000 times; the resilience was 76% as tested according to the GB/T1681 test method. The tensile strength after heat aging at 70 ℃/70h according to GB/T3512 is 24.2MPa, the elongation at break is 479%, and the hardness is changed by +2ShA.
Example 3
The example provides a rubber composition and a preparation method thereof, wherein the rubber composition comprises the following components in mass percent:
the preparation method of this example 3 is the same as that of example 1.
The rubber composition of the example is tested according to a GB/T528 test method, the tensile strength is 26.2MPa, the elongation at break is 496%, the hysteresis loss angle is 2.52 degrees by using an Instron material dynamic stiffness tester, and the rubber composition is tested according to a GB/T13934 test method, wherein the De mattia endurance fatigue times are more than 2080000 times; the rebound resilience was 67% as tested according to GB/T1681 test method. The tensile strength after heat aging at 70 ℃/70h according to GB/T3512 is 23.2MPa, the elongation at break is 459%, and the hardness is changed by +2ShA.
Comparative example 1
Substantially the same as in example 1, the only difference is that: the natural rubber was SCR10 standard rubber (available from Vietnam) without BR and added in an amount of 100kg.
The rubber composition of the example is tested according to a GB/T528 test method, the tensile strength of the rubber composition is 24.6MPa, the elongation at break is 496%, the hysteresis loss angle measured by an Instron material dynamic stiffness tester is 5.25 degrees, and the rubber composition is tested according to a GB/T13934 test method, wherein the De mattia endurance fatigue times are greater than 1100000 times; the resilience was 68% as tested according to GB/T1681 test method. The tensile strength after heat aging at 70 ℃/70h according to GB/T3512 is 22.3MPa, the elongation at break is 436%, and the hardness is changed by +4ShA. It can be seen that the combination of high cis BR and RSS1 results in a rubber material with significantly enhanced rebound resilience and significantly reduced hysteresis loss angle.
Comparative example 2
Substantially the same as in example 1, the only difference is that: equivalent substitution (30 kg) was made using N550 carbon black (available from Euro-Hiron, specific surface area about 40m 2/g, oil absorption value about 120mL/100g, screen residue less than or equal to 300 ppm).
The rubber composition of the example is tested according to a GB/T528 test method, the tensile strength of the rubber composition is 27.5MPa, the elongation at break is 514.6%, the hysteresis loss angle measured by an Instron material dynamic stiffness tester is 5.56 degrees, and the rubber composition is tested according to a GB/T13934 test method, wherein the De mattia endurance fatigue times are more than 960000 times; the resilience was 65% as measured according to GB/T1681 test method. The tensile strength after heat aging at 70 ℃/70h according to GB/T3512 is 26.3MPa, the elongation at break is 452%, and the hardness is changed by +4ShA. It can be seen that the light source is,Compared with the use of N550, the HS 25 can obtain smaller loss angle, and has better elasticity, namely smaller dynamic hardening effect; at the same time, the mechanical strength of the rubber is better maintained.
Comparative example 3
Substantially the same as in example 1, the only difference is that: equivalent substitution (30 kg) was made using N990 carbon black (available from Euro-Arron, specific surface area about 10m 2/g, oil absorption value about 40mL/100g, screen residue less than or equal to 300 ppm).
The rubber composition of the embodiment is tested according to a GB/T528 test method, the tensile strength is 16.5MPa, the elongation at break is 427%, the hysteresis loss angle is 1.66 degrees by using an Instron material dynamic stiffness tester, and the rubber composition is tested according to a GB/T13934 test method, wherein the De mattia endurance fatigue times are more than 1260000 times; the resilience was 79% as tested according to the GB/T1681 test method. The tensile strength after heat aging at 70 ℃/70h according to GB/T3512 is 13.2MPa, the elongation at break is 365%, and the hardness is +4ShA. It can be seen that the light source is,HS 25 can be used with a smaller loss angle, i.e., smaller dynamic stiffening effects, than N990; the tensile strength of the rubber is higher, and the dynamic fatigue durability is better.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (8)
1. A rubber composition comprising the following components: rubber matrix, reinforcing filler, anti-aging agent, paraffin, active agent and vulcanization system, and is characterized in that:
The vulcanization system comprises sulfur, an accelerator and a sulfur carrier, wherein the mass ratio of the sulfur to the accelerator to the sulfur carrier is 1:0.25-2.0:0.12-0.80, and the sulfur carrier is 1, 1-dithiobiscaprolactam;
The rubber matrix is composed of natural rubber and cis-1, 4-polybutadiene rubber, the natural rubber is first-grade tobacco flake rubber, the weight average molecular weight of the cis-1, 4-polybutadiene rubber is 200000-400000, and the feeding mass ratio of the natural rubber to the cis-polybutadiene rubber is 1:0.10-0.45;
The reinforcing filler is carbon black which is European and open engineering carbon group HS25；
The feeding mass ratio of the carbon black to the rubber matrix is 0.3-0.5:1;
The rubber composition comprises, by weight, 70-90 parts of natural rubber, 10-30 parts of cis-1, 4-polybutadiene rubber, 20-70 parts of carbon black, 2.0-5.0 parts of an anti-aging agent, 3.0-5.0 parts of paraffin wax, 5.0-9.0 parts of an active agent, 2.0-4.0 parts of sulfur, 1.0-4.0 parts of an accelerator and 0.5-1.5 parts of a sulfur carrier, wherein the total amount of the natural rubber and the cis-1, 4-polybutadiene rubber is 100 parts.
2. The rubber composition according to claim 1, wherein: the rubber composition comprises, by weight, 70-85 parts of natural rubber, 15-30 parts of cis-1, 4-polybutadiene rubber, 25-45 parts of carbon black, 3.0-5.0 parts of an anti-aging agent, 3.0-4.0 parts of paraffin wax, 6.0-8.0 parts of an active agent, 2.0-4.0 parts of sulfur, 1.5-3.5 parts of an accelerator and 0.5-1.0 part of a sulfur carrier.
3. The rubber composition according to claim 1 or 2, wherein: the antioxidant is one or a combination of more selected from ketoamine antioxidants, diphenylamine derivative antioxidants, p-phenylenediamine derivative antioxidants, environment-friendly hindered phenol antioxidants and hindered diphenol antioxidants; and/or the active agent is an inorganic active agent and/or an organic active agent, wherein the inorganic active agent comprises zinc oxide, the organic active agent is stearic acid, and the paraffin is microcrystalline paraffin.
4. The rubber composition according to claim 1, wherein: the sulfur is insoluble sulfur, and the accelerator is one or a combination of more selected from thiazole accelerators, sulfenamide accelerators, thiuram accelerators and guanidine accelerators.
5. The rubber composition according to claim 1, wherein: the rubber composition comprises the following components in parts by weight:
6. a process for producing the rubber composition as claimed in any one of claims 1 to 5, characterized in that: the preparation method comprises the following steps:
Adding other components except the vulcanization system into an internal mixer for shearing and mixing, wherein the mixing temperature is not more than 145 ℃, discharging tablets, cooling and standing to obtain master batch;
mixing the master batch and the vulcanization system, carrying out mixing, wherein the mixing temperature is not higher than 100 ℃, discharging the sheet to obtain a mixed rubber mixture, standing, and carrying out vulcanization to obtain the rubber composition.
7. The method for producing a rubber composition according to claim 6, wherein: the parking time before the master batch is obtained is 20-30h, and the parking time before the master batch is vulcanized is 5-20h; and/or, the vulcanization is carried out at 155-165 ℃, and the vulcanization time of the vulcanization is 5-15min.
8. Use of a rubber composition according to any one of claims 1 to 5 for the preparation of an automotive suspension bushing.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11172145A (en) * | 1997-12-15 | 1999-06-29 | Tokai Carbon Co Ltd | Carbon black for heat resistant and vibration resistant rubber, and rubber composition |
| CN105315511A (en) * | 2014-07-31 | 2016-02-10 | 株洲时代新材料科技股份有限公司 | Natural rubber and butadiene rubber blend and preparation method therefor and application thereof |
| CN108484994A (en) * | 2018-04-04 | 2018-09-04 | 江苏骆氏减震件有限公司 | A kind of natural rubber composition material and its preparation method and application |
| CN108623855A (en) * | 2017-03-29 | 2018-10-09 | 保定威奕汽车有限公司 | Damping sizing material and preparation method thereof and engine mounting and automobile |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11172145A (en) * | 1997-12-15 | 1999-06-29 | Tokai Carbon Co Ltd | Carbon black for heat resistant and vibration resistant rubber, and rubber composition |
| CN105315511A (en) * | 2014-07-31 | 2016-02-10 | 株洲时代新材料科技股份有限公司 | Natural rubber and butadiene rubber blend and preparation method therefor and application thereof |
| CN108623855A (en) * | 2017-03-29 | 2018-10-09 | 保定威奕汽车有限公司 | Damping sizing material and preparation method thereof and engine mounting and automobile |
| CN108484994A (en) * | 2018-04-04 | 2018-09-04 | 江苏骆氏减震件有限公司 | A kind of natural rubber composition material and its preparation method and application |
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