CN117070006B - Low-temperature-resistant crystallization-resistant butadiene rubber composition, preparation method thereof and rubber sealing product - Google Patents
Low-temperature-resistant crystallization-resistant butadiene rubber composition, preparation method thereof and rubber sealing product Download PDFInfo
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- CN117070006B CN117070006B CN202311340830.4A CN202311340830A CN117070006B CN 117070006 B CN117070006 B CN 117070006B CN 202311340830 A CN202311340830 A CN 202311340830A CN 117070006 B CN117070006 B CN 117070006B
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- 229920002857 polybutadiene Polymers 0.000 title claims abstract description 149
- 239000005062 Polybutadiene Substances 0.000 title claims abstract description 148
- 239000000203 mixture Substances 0.000 title claims abstract description 64
- 238000002425 crystallisation Methods 0.000 title claims abstract description 50
- 230000008025 crystallization Effects 0.000 title claims abstract description 50
- 229920001971 elastomer Polymers 0.000 title claims description 33
- 239000005060 rubber Substances 0.000 title claims description 33
- 238000007789 sealing Methods 0.000 title claims description 22
- 238000002360 preparation method Methods 0.000 title claims description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 23
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 23
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 14
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 12
- 239000004902 Softening Agent Substances 0.000 claims abstract description 9
- 239000011787 zinc oxide Substances 0.000 claims abstract description 8
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008117 stearic acid Substances 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 28
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 8
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 239000003502 gasoline Substances 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims 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 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 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 3
- 229960002447 thiram Drugs 0.000 claims description 3
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims description 2
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims description 2
- 230000003311 flocculating effect Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 9
- 238000012360 testing method Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000010092 rubber production Methods 0.000 abstract description 2
- 229920002379 silicone rubber Polymers 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- YCOHEPDJLXZVBZ-UHFFFAOYSA-N 2-benzylsulfonyl-1-(1h-indol-3-yl)-1h-isoquinoline Chemical compound C1=CC2=CC=CC=C2C(C=2C3=CC=CC=C3NC=2)N1S(=O)(=O)CC1=CC=CC=C1 YCOHEPDJLXZVBZ-UHFFFAOYSA-N 0.000 description 4
- 101100532856 Arabidopsis thaliana SDRA gene Proteins 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005303 weighing Methods 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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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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 belongs to the technical field of rubber production, and particularly relates to a low-temperature-resistant crystallization-resistant butadiene rubber composition, which comprises the following components: 100PHR of composite butadiene rubber, 30-70PHR of reinforcing agent, 10-40PHR of softening agent, 4-6PHR of zinc oxide, 1-3PHR of stearic acid, 1-5PHR of anti-aging agent, 0.5-3PHR of sulfur and 0.5-2PHR of accelerator; wherein the composite butadiene rubber is copolymer butadiene rubber or a blend of rare earth butadiene rubber and copolymer butadiene rubber, and the mass content of the copolymer butadiene rubber is 30-100%; the mass content of the comonomer in the copolymer butadiene rubber is 5-20%, and the comonomer is isoprene. The invention provides a low temperature resistant crystallization resistant butadiene rubber composition, which has the advantages that the glass transition temperature (DMA test loss factor peak temperature) is less than-70 ℃, the elasticity is better at the temperature of-60 ℃, and the low temperature resistant performance of the existing rare earth butadiene rubber material can be expanded to about 35-50 ℃; but also has lower cost of raw materials.
Description
Technical Field
The invention belongs to the technical field of rubber production, and particularly relates to a low-temperature-resistant crystallization-resistant butadiene rubber composition, a preparation method thereof and a rubber sealing product.
Background
The rubber sealing product is a product for realizing low-temperature gas or liquid sealing of rubber through elasticity of rubber, and is an indispensable product in industrial application. At present, according to different application environments, rubber sealing product materials comprise silicon rubber (glass transition temperature-120 ℃), fluororubber (glass transition temperature-30 ℃), butadiene rubber (glass transition temperature-80 to-105 ℃), ethylene propylene diene monomer rubber (glass transition temperature-35 to-60 ℃), natural rubber (glass transition temperature 65 to-70 ℃), nitrile rubber (glass transition temperature 25 to-60 ℃), chloroprene rubber (glass transition temperature-40 to-50 ℃) and embrittlement temperature-35 ℃) and the like. As is clear from the glass transition temperature, the rubber with better low temperature resistance is butadiene rubber and silicon rubber.
However, crystallization is another important factor affecting rubber elasticity and also an important cause for lowering low-temperature sealing performance, because crystallization tends to cause volume shrinkage of rubber, and compressive stress is reduced, thereby lowering sealing performance. In general, it is difficult to achieve sealing at a temperature below-50℃with a glass transition temperature higher than-50℃or due to crystallization behavior. For example: the glass transition temperature of butyl rubber is about minus 60 ℃ and the glass transition temperature of natural rubber is between minus 65 ℃ and minus 70 ℃, but the butyl rubber and the natural rubber have certain crystallization capability, so that the low-temperature sealing is affected to a certain extent. The silicon rubber has a glass transition temperature of-120 ℃, has excellent low temperature resistance and aging resistance, but has crystallization capability at low temperature (Wang Xin, li Chaoqin; crystallization behavior and dynamics research of silicon rubber, rubber industry, 2023,70 (5), 330-335) and has higher cost.
Therefore, development of rubber materials with low glass transition temperature and effective crystallization resistance is of great significance to development and application of low-temperature-resistant sealing products.
Disclosure of Invention
Rubber sealing articles require good elasticity at low temperatures, ensuring their low temperature sealing properties, and therefore require rubber materials having low glass transition temperatures and being unable to crystallize. The glass transition temperature of butadiene rubber is at least about-105 ℃, but obvious crystallization occurs between-30 ℃ and-50 ℃; in order to solve the defects in the prior art, the invention provides a low-temperature-resistant crystallization-resistant butadiene rubber composition, and the glass transition temperature of the chemically modified butadiene rubber is lower than-90 ℃ (DSC method), so that the low-temperature-resistant performance of the existing rubber product is expanded, and meanwhile, the crystallization-resistant performance of the butadiene rubber is very strong, so that the glass transition temperature (between-95 ℃ and 103 ℃ in DSC method and between-70 ℃ and 90 ℃ in DMA method) crystallization-resistant rubber material can be prepared by compounding the chemically modified butadiene rubber and the butadiene rubber with low glass transition temperature, and the low-temperature-resistant crystallization-resistant butadiene rubber composition is suitable for rubber sealing products below-60 ℃.
The technical effects to be achieved by the invention are realized by the following technical scheme:
the low temperature resistant crystallization resistant butadiene rubber composition comprises the following components:
100PHR composite butadiene rubber
Reinforcing agent 30-70PHR
Softener 10-40PHR
Zinc oxide 4-6PHR
Stearic acid 1-3PHR
Anti-aging agent 1-5PHR
Sulfur 0.5-3PHR
0.5-2PHR promoter;
wherein the composite butadiene rubber is copolymer butadiene rubber or a blend of rare earth butadiene rubber and copolymer butadiene rubber, and the mass content of the copolymer butadiene rubber is 30-100%; the mass content of the comonomer in the copolymer butadiene rubber is 5-20%, and the comonomer is isoprene.
Further, the reinforcing agent is carbon black or a mixture of carbon black and other fillers, and the mass ratio of the other fillers is not more than 50%.
Further, the other filler is one or more of talcum powder, calcium carbonate, clay, mica powder, kaolin and montmorillonite.
Further, the softener is one or more of aromatic oil, naphthenic oil and paraffinic oil.
Further, the anti-aging agent is one or more of amine anti-aging agent, phenol anti-aging agent and phosphite anti-aging agent.
Further, the accelerator is one or more of sulfenamide TBBS, sulfenamide CBS, guanidine DPG and thiuram TMTD.
The preparation method of the low-temperature-resistant crystallization-resistant butadiene rubber composition comprises the following steps:
s10, preparing composite butadiene rubber through solution mixing or solution mixing;
s20, adding a reinforcing agent, mixing, and adding a softening agent;
s30, adding all auxiliary agents except vulcanizing agents, mixing and discharging glue;
s40, cooling the discharged rubber, adding a vulcanizing agent, uniformly mixing, and vulcanizing to prepare the product.
Further, in the step S10, when the compound butadiene rubber is prepared by solution mixing, the method comprises the steps of:
s11, dissolving rare earth butadiene rubber and copolymerized butadiene rubber in a solvent according to a mass ratio;
and S12, precipitating by using an ethanol solution, and drying to obtain the composite butadiene rubber.
Further, in the step S11, the solvent is one or more of hexane, cyclohexane, benzene, toluene, and gasoline.
Further, in the step S10, the composite butadiene rubber is formed by uniformly mixing rare earth butadiene rubber and copolymer butadiene rubber in an internal mixer according to mass proportion; wherein the rotation speed of mixing the rare earth butadiene rubber and the copolymer butadiene rubber is 40rpm-80rpm, the temperature is 40-60 ℃ and the time is 3-8 min.
The rubber sealing product is prepared from the low-temperature-resistant crystallization-resistant butadiene rubber composition and has good low-temperature-resistant and sealing properties.
In summary, the present invention has at least the following advantages:
1. the low temperature resistant crystallization resistant butadiene rubber composition has the glass transition temperature of less than-90 ℃ (DSC method; DMA rule of-70 ℃), and has better elasticity at-60 ℃, so that the low temperature resistant performance of the existing rare earth butadiene rubber material can be expanded to about 35-50 ℃ at low temperature, and the low temperature resistant butadiene rubber composition is one of carbon-based polymers with the best low temperature resistant performance at present.
2. Butadiene-based rubber is one of the lowest cost rubbers at present (natural rubber, 1.3 ten thousand yuan/ton, silicon rubber, more than 2 ten thousand yuan/ton, ethylene propylene rubber, about 2-3 ten thousand yuan/ton, chloroprene rubber, 4-5 ten thousand yuan/ton, nitrile rubber, 2.0 ten thousand yuan/ton, hydrogenated nitrile rubber, 30 ten thousand yuan/ton, butadiene rubber, about 1.05 ten thousand yuan/ton, styrene-butadiene rubber, 1.2 ten thousand yuan/ton, isoprene rubber, 1.3 ten thousand yuan/ton) and has a lower glass transition temperature (only higher than silicon rubber), so the low-temperature resistant crystallization resistant butadiene rubber composition provided by the invention has excellent low-temperature resistant performance and lower raw material cost.
Detailed Description
For a better illustration of the objects, technical solutions and advantages of the present invention, the present invention will be more fully described with reference to the following specific examples. The invention provides a preferred embodiment. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used, unless otherwise specified, are commercially available.
As used herein, any reference to "one embodiment" or "an embodiment" means that a particular element, feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment.
Unless defined otherwise herein, scientific and technical terms used in connection with the present disclosure shall have the meanings commonly understood by one of ordinary skill in the art. Furthermore, unless the context requires otherwise, singular terms shall include the plural and plural terms shall include the singular.
In a first aspect, the present invention provides a low temperature resistant and crystallization resistant butadiene rubber composition comprising: 100PHR of composite butadiene rubber, 30-70PHR of reinforcing agent, 10-40PHR of softening agent, 4-6PHR of zinc oxide, 1-3PHR of stearic acid, 1-5PHR of anti-aging agent, 0.5-3PHR of sulfur and 0.5-2PHR of accelerator; wherein the composite butadiene rubber is copolymer butadiene rubber or a blend of rare earth butadiene rubber and copolymer butadiene rubber, and the mass content of the copolymer butadiene rubber is 30-100%.
Further, the percentage mass content of the comonomer in the copolymer butadiene rubber is 5-20%, and the comonomer is isoprene. The reinforcing agent is carbon black or a mixture of the carbon black and other fillers, and the mass ratio of the other fillers is not more than 50%; the other filler is one or more of talcum powder, calcium carbonate, clay, mica powder, kaolin and montmorillonite. The softener is one or more of aromatic hydrocarbon oil, naphthenic hydrocarbon oil and paraffinic hydrocarbon oil. The aging inhibitor is one or more of amine aging inhibitor, phenol aging inhibitor and phosphite aging inhibitor. The promoter is one or more of sulfenamide TBBS, sulfenamide CBS, guanidine DPG and thiuram TMTD.
In a second aspect, the invention also provides a preparation method of the low-temperature-resistant crystallization-resistant butadiene rubber composition, which comprises the following steps:
s10, preparing composite butadiene rubber through solution mixing or solution mixing;
s20, adding a reinforcing agent, mixing, and adding a softening agent;
s30, adding all auxiliary agents except vulcanizing agents, mixing and discharging glue;
s40, cooling the discharged rubber, adding a vulcanizing agent, uniformly mixing, and vulcanizing to prepare the product.
Further, in the step S10, when the compound butadiene rubber is prepared by solution mixing, the steps of:
s11, dissolving rare earth butadiene rubber and copolymerized butadiene rubber in a solvent according to a mass ratio; further, the solvent is one or more of hexane, cyclohexane, benzene, toluene and gasoline.
And S12, precipitating by using an ethanol solution, and drying to obtain the composite butadiene rubber.
Further, in the step S10, the composite butadiene rubber can be prepared by uniformly mixing rare earth butadiene rubber and copolymer butadiene rubber in an internal mixer according to mass proportion; wherein, the rotation speed of mixing the rare earth butadiene rubber and the copolymerization butadiene rubber is 40rpm-80rpm, the temperature is 40-60 ℃ and the time is 3-8 min.
In a third aspect, the invention also provides a rubber sealing product, which is prepared from the low-temperature-resistant crystallization-resistant butadiene rubber composition and has good low-temperature-resistant and sealing properties; further, the rubber sealing product is a low temperature resistant O-shaped sealing ring or a low temperature resistant tire.
In the following specific examples, the main raw materials and main equipment sources used therein are as follows:
butadiene rubber: sinkiang Dushanzi petrochemical Co., ltd;
reinforcing agent: shanghai Kabo chemical Co., ltd;
calcium carbonate: yingge porcelain (Tuhu Co., ltd.)
Softening agent: ningbo Hansheng chemical Co., ltd;
zinc oxide: the Changzhou kyls chemical industry Co., ltd;
stearic acid: the Changzhou kyls chemical industry Co., ltd;
anti-aging agent: the Changzhou kyls chemical industry Co., ltd;
sulfur: the Changzhou kyls chemical industry Co., ltd;
and (3) an accelerator: the Changzhou kyls chemical industry Co., ltd.
The compositions of the low temperature resistant and crystallization resistant butadiene rubber compositions in the examples are as follows: 100PHR of composite butadiene rubber, 30-70PHR of reinforcing agent, 10-40PHR of softening agent, 4-6PHR of zinc oxide, 1-3PHR of stearic acid, 1-5PHR of anti-aging agent, 0.5-3PHR of sulfur and 0.5-2PHR of accelerator; wherein the composite butadiene rubber is copolymer butadiene rubber or a blend of rare earth butadiene rubber and copolymer butadiene rubber, and the mass content of the copolymer butadiene rubber is 30-100%. Further, the percentage mass content of the comonomer in the copolymer butadiene rubber is 5-20%, and the comonomer is isoprene. The reinforcing agent is preferably N330 carbon black or N660 carbon black or a mixture of carbon black and calcium carbonate, the softening agent is preferably environment-friendly aromatic hydrocarbon oil, the anti-aging agent is preferably 6PPD and RD, and the accelerator is preferably CBS. Specifically, the compositions of the low temperature resistant and crystallization resistant butadiene rubber compositions in each example are shown in Table 1, and the compositions of the butadiene rubber compositions in each comparative example are shown in Table 2.
Table 1 parts of components per 100 parts by mass of the butadiene rubber composition
Table 2 comparative examples parts per 100 parts by mass of the components in the butadiene rubber composition
The components in tables 1 and 2 are noted below,
BR9000: BR9000 brand rare earth butadiene rubber;
BR9101N: BR9101N brand rare earth butadiene rubber;
IBR1: copolymerized butadiene rubber with the comonomer isoprene content of 18 percent by mass;
IBR2: copolymerized butadiene rubber with 8 percent of comonomer isoprene by mass;
N330/N660: carbon black;
ZnO: zinc oxide;
SA: stearic acid;
6PPD: n- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine;
RD: an anti-aging agent RD;
TDAE: environmental protection aromatic hydrocarbon oil;
s: sulfur;
CBS: n-cyclohexyl-2-benzothiazole sulfenamide;
the IBR1 and the IBR2 are made of laboratory self-made materials, and the main difference is that the mass percentage of the comonomer isoprene in the IBR1 is 18 percent, and the mass percentage of the comonomer isoprene in the IBR2 is 8 percent; specifically, the preparation method of the IBR1 and the IBR2 comprises the following steps:
1. butadiene and isoprene were dissolved in a hexane solvent in a mass ratio, and then added into a reaction kettle, the temperature was kept at 40 ℃, and triethylaluminum was injected into the reaction kettle to break impurities for 5 minutes at 0.1M.
2. Heating to 50 ℃, sequentially adding catalyst such as triisobutylaluminum 0.1M, neodecanoic acid neodymium 0.1M, diisobutylaluminum chloride 0.1M and the like, and reacting for 2 hours.
3. Cooling to 40 ℃, putting the polymerized rubber solution into an ethanol solution of an antioxidant 264, terminating the reaction, flocculating the IBR polymer, air-drying the flocculated IBR polymer, and drying in a vacuum drying oven to constant weight.
The preparation method of the low-temperature-resistant crystallization-resistant butadiene rubber composition comprises the following steps:
s10, dissolving rare earth butadiene rubber and copolymerized butadiene rubber in a hexane solvent according to a mass ratio, precipitating by using an ethanol solution, and drying; or weighing rare earth butadiene rubber and copolymerized butadiene rubber according to the mass ratio, mixing the rare earth butadiene rubber and the copolymerized butadiene rubber in an internal mixer at the rotating speed of 40-80 rpm and the temperature of 40-60 ℃ for 3-8 min to prepare the composite butadiene rubber; this step was omitted in the preparation of the butadiene rubber composition in the comparative example.
S20, adding a reinforcing agent, mixing for 2min, and adding a softening agent TDAE;
s30, adding all auxiliary agents except the vulcanizing agent, mixing for 1-3min, and discharging glue;
s40, cooling the discharged rubber on an open mill, adding a vulcanizing agent, uniformly mixing, and vulcanizing to prepare the product.
The butadiene rubber compositions prepared in each example and each comparative example were subjected to performance tests respectively with reference to the following criteria, in particular:
1. with reference to GB/T1681, each butadiene rubber composition was subjected to a rebound test, respectively;
2. with reference to GB/T529, each butadiene rubber composition was tested for tear strength;
3. referring to GB/T531, each butadiene rubber composition was tested for hardness at room temperature and-50℃respectively;
4. with reference to GB/T528, each butadiene rubber composition was tested for tensile strength and elongation at room temperature and-50℃respectively;
5. with reference to ISO 4664, each butadiene rubber composition was subjected to a glass transition temperature (DMA method) test;
6. with reference to GB/T19466, each butadiene rubber composition was subjected to a crystallization temperature (DSC method) test, respectively;
the results of the performance test of each butadiene rubber composition are shown in tables 3 and 4.
TABLE 3 rebound, tear Strength, hardness, tensile Strength and elongation of the respective butadiene rubber compositions
TABLE 4 glass transition temperature, crystallization temperature and Low temperature use temperature of the respective butadiene rubber compositions
Note that: the minimum use temperature is based on the glass transition end temperature or the onset crystallization temperature.
As can be seen from tables 3 and 4, the copolymer butadiene rubber and the composite material thereof have good room temperature mechanical properties. However, the conventional butadiene rubbers BR9101N and BR9000 have a remarkable crystallization ability at low temperatures, resulting in hardening of the rubber and a decrease in low temperature resistance. The low-temperature crystallization capability of the copolymer butadiene rubber and the composite material of the copolymer butadiene rubber and the rare earth butadiene rubber prepared by the invention is obviously inhibited, because the crystallization of the butadiene rubber is required to be carried out through nucleation and growth, the copolymer butadiene rubber and the common butadiene rubber can be mixed at molecular level by adding the copolymer butadiene rubber which is not crystallized but is completely compatible into the crystallized common butadiene rubber, the distance between molecular chains is increased by diluting the common butadiene rubber, and meanwhile, the probability and crystallization capability of molecular chain movement and nucleation are reduced by the higher molecular weight and viscosity of the copolymer rubber. In the formula, the rubber with weaker crystallization capability forms a gel network under the action of a cross-linking agent, so that the crystallizable common butadiene rubber is fixed in the middle of a non-crystallizable modified butadiene rubber molecule to lose crystallization capability. Therefore, the crystallinity of the butadiene rubber composition prepared by adding the copolymer butadiene rubber is obviously improved, basically does not crystallize in a low-temperature environment, has better elasticity below-60 ℃, and can expand the low-temperature resistance of the conventional rare earth butadiene rubber to about 35-50 ℃.
According to the technical scheme of the embodiment, the invention provides the low-temperature-resistant crystallization-resistant butadiene rubber composition, which has the advantages that the glass transition temperature (DMA test loss factor peak temperature) is less than-70 ℃, the elasticity is better at the temperature of-60 ℃, and the low-temperature resistance of the existing material can be expanded to be about 35-50 ℃; but also has lower cost of raw materials. The invention also provides a preparation method suitable for the low-temperature-resistant crystallization-resistant butadiene rubber composition, and a rubber sealing product prepared by using the low-temperature-resistant crystallization-resistant butadiene rubber composition.
It will be apparent to one of ordinary skill in the art that embodiments of the present disclosure may be practiced without these specific details. In other instances, well-known features have not been described in detail so as not to unnecessarily obscure the present invention. It is intended that all alternatives, substitutions, modifications, and equivalents as would be apparent to one of ordinary skill in the art be included within the scope of the present disclosure. In accordance with the present disclosure, all of the compounds/compositions disclosed herein, as well as methods of making, using and using the same, can be made and practiced without undue experimentation.
Although the compounds/compositions and methods of this disclosure have been described in terms of specific embodiments, it will be apparent to those of skill in the art that variations may be applied to the formulations, compounds or compositions and/or methods and in the steps or in the sequence of steps of the methods described herein without departing from the spirit and scope of the inventive concepts of this disclosure.
While the invention has been described in conjunction with the specific embodiments above, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, all such alternatives, modifications, and variations are included within the spirit and scope of the following claims.
Claims (10)
1. A low-temperature-resistant crystallization-resistant butadiene rubber composition is characterized by comprising the following components:
100PHR composite butadiene rubber
Reinforcing agent 30-70PHR
Softener 10-40PHR
Zinc oxide 4-6PHR
Stearic acid 1-3PHR
Anti-aging agent 1-5PHR
Sulfur 0.5-3PHR
0.5-2PHR promoter;
wherein the composite butadiene rubber is a blend of rare earth butadiene rubber and copolymer butadiene rubber, and the mass content of the copolymer butadiene rubber is 30-70%; the comonomer type in the copolymer butadiene rubber is isoprene, and the percentage mass content of the comonomer is 8% or 18%;
the preparation method of the copolymer butadiene rubber comprises the following steps:
dissolving butadiene and isoprene in a hexane solvent according to a mass ratio, then adding the mixture into a reaction kettle, preserving heat at 40 ℃, and crushing impurities by pricking triethylaluminum for 5 minutes in 0.1M;
heating to 50 ℃, sequentially adding 0.1M triisobutylaluminum, 0.1M neodecanoic acid neodymium and 0.1M diisobutylchloroaluminum, and reacting for 2 hours;
cooling to 40 ℃, putting the polymerized rubber solution into an ethanol solution of an antioxidant 264, terminating the reaction, flocculating the polymer, air-drying the flocculated polymer, and drying in a vacuum drying oven to constant weight;
and the softener is one or more of aromatic hydrocarbon oil, naphthenic hydrocarbon oil and paraffinic hydrocarbon oil.
2. The low temperature resistant and crystallization resistant butadiene rubber composition according to claim 1, wherein the reinforcing agent is carbon black or a mixture of carbon black and other fillers, and the mass ratio of the other fillers is not more than 50%.
3. The low temperature resistant and crystallization resistant butadiene rubber composition according to claim 2, wherein the other filler is one or more of talcum powder, calcium carbonate, mica powder, kaolin and montmorillonite.
4. The low temperature resistant crystallization resistant butadiene rubber composition according to claim 1, wherein the aging inhibitor is one or more of amine aging inhibitor, phenol aging inhibitor, phosphite aging inhibitor.
5. The low temperature resistant and crystallization resistant butadiene rubber composition according to claim 1, wherein the accelerator is one or more of sulfenamide TBBS, sulfenamide CBS, guanidine DPG, thiuram TMTD.
6. A process for preparing a low temperature resistant crystallization resistant butadiene rubber composition as defined in any one of claims 1-5, comprising the steps of:
s10, preparing composite butadiene rubber through solution mixing or melt mixing;
s20, adding a reinforcing agent, mixing, and adding a softening agent;
s30, adding all auxiliary agents except vulcanizing agents, mixing and discharging glue;
s40, cooling the discharged rubber, adding a vulcanizing agent, uniformly mixing, and vulcanizing to prepare the product.
7. The method for preparing a low temperature resistant and crystallization resistant butadiene rubber composition according to claim 6, wherein in the step S10, when preparing a composite butadiene rubber by solution mixing, comprising the steps of:
s11, dissolving rare earth butadiene rubber and copolymerized butadiene rubber in a solvent according to a mass ratio;
and S12, precipitating by using an ethanol solution, and drying to obtain the composite butadiene rubber.
8. The method for preparing a low temperature resistant and crystallization resistant butadiene rubber composition according to claim 7, wherein in the step S11, the solvent is one or more of hexane, cyclohexane, benzene, toluene and gasoline.
9. The method for preparing the low temperature resistant and crystallization resistant butadiene rubber composition according to claim 6, wherein in the step S10, the composite butadiene rubber is prepared by uniformly mixing rare earth butadiene rubber and copolymer butadiene rubber in an internal mixer according to a mass ratio;
wherein the rotation speed of mixing the rare earth butadiene rubber and the copolymer butadiene rubber is 40rpm-80rpm, the temperature is 40-60 ℃ and the time is 3-8 min.
10. A rubber sealing article prepared by using the low temperature resistant crystallization resistant butadiene rubber composition of any one of claims 1-5.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4409056A (en) * | 1978-09-12 | 1983-10-11 | Kuraray Co., Ltd. | Curable sealing composition |
| CN107652381A (en) * | 2017-09-26 | 2018-02-02 | 青岛瑞林材料科技有限公司 | A kind of preparation method of high-cis diene polymer |
| CN109942910A (en) * | 2019-03-21 | 2019-06-28 | 山东华聚高分子材料有限公司 | A kind of high flexing fatigue service life aviation sidewall rubber, preparation method and application |
| CN112812391A (en) * | 2021-02-05 | 2021-05-18 | 中国科学院青岛生物能源与过程研究所 | High-wet-skid-resistance tire tread rubber composite material and preparation method thereof |
| CN115230266A (en) * | 2021-04-23 | 2022-10-25 | 中国科学院大连化学物理研究所 | Multilayer structure wide-temperature-range oil-resistant sealing product and preparation method and application thereof |
| CN115678127A (en) * | 2022-11-07 | 2023-02-03 | 广东粤港澳大湾区黄埔材料研究院 | Sidewall rubber and preparation method and application thereof |
| CN116003884A (en) * | 2023-01-04 | 2023-04-25 | 中国科学院青岛生物能源与过程研究所 | Rubber composite material and preparation method thereof |
| CN116355295A (en) * | 2023-03-06 | 2023-06-30 | 山东昊华轮胎有限公司 | Inflammable and explosive product transport vehicle tread rubber composite material and preparation method and application thereof |
| CN116426043A (en) * | 2023-04-18 | 2023-07-14 | 青岛科技大学 | Phase-change energy-storage trans-butyl-pentyl rubber material with high crystallization melting temperature and preparation method thereof |
| CN116640367A (en) * | 2023-07-17 | 2023-08-25 | 保定三源橡胶有限公司 | High-wear-resistance coating rubber material for conveyor belt |
-
2023
- 2023-10-17 CN CN202311340830.4A patent/CN117070006B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4409056A (en) * | 1978-09-12 | 1983-10-11 | Kuraray Co., Ltd. | Curable sealing composition |
| CN107652381A (en) * | 2017-09-26 | 2018-02-02 | 青岛瑞林材料科技有限公司 | A kind of preparation method of high-cis diene polymer |
| CN109942910A (en) * | 2019-03-21 | 2019-06-28 | 山东华聚高分子材料有限公司 | A kind of high flexing fatigue service life aviation sidewall rubber, preparation method and application |
| CN112812391A (en) * | 2021-02-05 | 2021-05-18 | 中国科学院青岛生物能源与过程研究所 | High-wet-skid-resistance tire tread rubber composite material and preparation method thereof |
| CN115230266A (en) * | 2021-04-23 | 2022-10-25 | 中国科学院大连化学物理研究所 | Multilayer structure wide-temperature-range oil-resistant sealing product and preparation method and application thereof |
| CN115678127A (en) * | 2022-11-07 | 2023-02-03 | 广东粤港澳大湾区黄埔材料研究院 | Sidewall rubber and preparation method and application thereof |
| CN116003884A (en) * | 2023-01-04 | 2023-04-25 | 中国科学院青岛生物能源与过程研究所 | Rubber composite material and preparation method thereof |
| CN116355295A (en) * | 2023-03-06 | 2023-06-30 | 山东昊华轮胎有限公司 | Inflammable and explosive product transport vehicle tread rubber composite material and preparation method and application thereof |
| CN116426043A (en) * | 2023-04-18 | 2023-07-14 | 青岛科技大学 | Phase-change energy-storage trans-butyl-pentyl rubber material with high crystallization melting temperature and preparation method thereof |
| CN116640367A (en) * | 2023-07-17 | 2023-08-25 | 保定三源橡胶有限公司 | High-wear-resistance coating rubber material for conveyor belt |
Non-Patent Citations (2)
| Title |
|---|
| Evolution of crosslinking networks structure and thermo-oxidative aging behavior of unfilled NR/BR blends with TBIR as extra functional compatibilizer;Huafeng Shao等;《Polymer Testing》;第115卷;1-8 * |
| 丁二烯-异戊二烯共聚橡胶物理性能的研究;李今芳等;《特种橡胶制品》(第4期);1-4 * |
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