WO2015109789A1 - Composition de caoutchouc contenant un agent de couplage organosilane et du noir de carbone et son procédé de préparation - Google Patents
Composition de caoutchouc contenant un agent de couplage organosilane et du noir de carbone et son procédé de préparation Download PDFInfo
- Publication number
- WO2015109789A1 WO2015109789A1 PCT/CN2014/082692 CN2014082692W WO2015109789A1 WO 2015109789 A1 WO2015109789 A1 WO 2015109789A1 CN 2014082692 W CN2014082692 W CN 2014082692W WO 2015109789 A1 WO2015109789 A1 WO 2015109789A1
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- Prior art keywords
- rubber
- weight
- parts
- seconds
- carbon black
- Prior art date
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 87
- 239000005060 rubber Substances 0.000 title claims abstract description 86
- 239000006229 carbon black Substances 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 239000007822 coupling agent Substances 0.000 title claims abstract description 24
- 150000001282 organosilanes Chemical class 0.000 title abstract description 19
- 238000002360 preparation method Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 46
- 230000008569 process Effects 0.000 claims abstract description 37
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 239000012190 activator Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 97
- 239000003963 antioxidant agent Substances 0.000 claims description 28
- 230000003078 antioxidant effect Effects 0.000 claims description 24
- 239000011593 sulfur Substances 0.000 claims description 24
- 229910052717 sulfur Inorganic materials 0.000 claims description 24
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 238000010074 rubber mixing Methods 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 5
- 238000004073 vulcanization Methods 0.000 claims description 5
- 244000043261 Hevea brasiliensis Species 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 229920003052 natural elastomer Polymers 0.000 claims description 4
- 229920001194 natural rubber Polymers 0.000 claims description 4
- HKMVWLQFAYGKSI-UHFFFAOYSA-N 3-triethoxysilylpropyl thiocyanate Chemical compound CCO[Si](OCC)(OCC)CCCSC#N HKMVWLQFAYGKSI-UHFFFAOYSA-N 0.000 claims description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 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
- 229920003051 synthetic elastomer Polymers 0.000 claims description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims 1
- 239000005062 Polybutadiene Substances 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- 125000002897 diene group Chemical group 0.000 claims 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims 1
- 229920002857 polybutadiene Polymers 0.000 claims 1
- 230000003712 anti-aging effect Effects 0.000 abstract description 10
- 238000005096 rolling process Methods 0.000 abstract description 9
- 238000013329 compounding Methods 0.000 abstract description 5
- 238000005299 abrasion Methods 0.000 abstract description 3
- 239000005864 Sulphur Substances 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 19
- 239000011787 zinc oxide Substances 0.000 description 19
- 235000021355 Stearic acid Nutrition 0.000 description 17
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 17
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 17
- 239000008117 stearic acid Substances 0.000 description 17
- 239000004200 microcrystalline wax Substances 0.000 description 13
- 235000019808 microcrystalline wax Nutrition 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 230000020169 heat generation Effects 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 10
- 239000003292 glue Substances 0.000 description 10
- 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 9
- 230000001965 increasing effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000010077 mastication Methods 0.000 description 6
- 230000018984 mastication Effects 0.000 description 6
- 150000001993 dienes Chemical class 0.000 description 5
- 229920003049 isoprene rubber Polymers 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 241000907903 Shorea Species 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- -1 diamine compound Chemical class 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- WORCCYVLMMTGFR-UHFFFAOYSA-M loxoprofen sodium Chemical compound [Na+].C1=CC(C(C([O-])=O)C)=CC=C1CC1C(=O)CCC1 WORCCYVLMMTGFR-UHFFFAOYSA-M 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method 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
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/005—Methods for mixing in batches
-
- 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
-
- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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
Definitions
- the invention relates to the field of rubber, in particular to the field of tire manufacture.
- One of the basic characteristics of rubber is: In the process of use, energy loss occurs due to the hysteresis loss of the rubber compound, and at the same time, it is converted into heat, and heat generation reduces the service life of the tire. Under the premise of not losing the basic properties of the rubber material such as wear resistance and physical properties, reducing the heat generation of the rubber compound will increase the use of the tire.
- the patent "Rubber Composition” discloses the mixing of natural rubber with silica/organosilane coupling agent to make the composition low in heat generation and wear resistance;
- Patent “Rubber Composition” (publication number CN1322223A) A diolefin polymer containing white carbon black is disclosed for reducing the rolling resistance of the tire;
- the patent “rubber composition and the pneumatic tire prepared from the rubber composition” (publication number CN1205016A), the release of natural rubber Or a diene rubber with white carbon black and a specific silane coupling agent to prepare a low heat generating, low rolling resistance tire.
- the above-mentioned patents all use a polymer mixed with a silica/silane coupling agent, and the rubber composition prepared by the method is inferior in abrasion resistance, particularly in truck tires.
- the rubber composition of the present invention introduces an organosilane coupling agent to make the carbon black interact more strongly with the diene polymer, the wear resistance is improved, the heat generation is lowered, and the rolling resistance of the tire is lowered.
- Patent "Use of surface treated carbon black to reduce compound lag and tire rolling resistance in elastomers and to improve wet skid resistance” discloses the interaction between surface treated carbon black and polymer, The carbon black needs to be treated with an oxidizing agent, preferably a diamine compound. Such a treatment method has a residual or unreacted oxidizing agent present in the rubber composition formulation, affecting the vulcanization time of the rubber mixture, especially shortening the scorch time and affecting the processing safety. Sex.
- organosilane coupling agent of the invention has no effect on the vulcanization characteristics of the formulation, and the surface treatment of the carbon black is directly completed in the process of processing, and it is not necessary to separately treat the carbon black, which is more convenient for processing.
- the patent "A Process for Increasing the Dispersion of Silica Black” (Application No. CN101786298A) discloses a process for preparing a masterbatch using a polymer and a silica, an organosilane coupling agent, and does not involve how to improve carbon black and polymer. The process of interaction. By using the mixing process of the invention, an organosilane coupling agent is introduced into the rubber composition, thereby enhancing the interaction between the polymer and the carbon black, and improving the performance of the rubber compound. Summary of the invention
- the present invention is intended to provide a rubber composition reinforced with carbon black and a method for producing the same, which has the advantages of high wear resistance, low heat build-up, and low rolling resistance.
- the rubber composition contains a diene polymer, carbon black, a certain proportion of an organosilane coupling agent and a corresponding compounding agent, and the polymer is pre-mixed with a carbon black and an organosilane coupling agent to form a masterbatch.
- the interaction with carbon black, after vulcanization, can improve the wear resistance of the rubber compound, reduce the heat generation performance of the rubber compound, and improve the dynamic performance of the rubber compound.
- the wear resistance of the tire can be improved and the rolling resistance can be reduced.
- the process advantages of the invention are as follows: Under the action of the organosilane coupling agent, the effect of the carbon black particles is reduced during the mixing process, the effect between the carbon black and the polymer is increased, and the heat generation of the rubber compound is reduced.
- the present invention relates to a rubber composition comprising: a diene-based polymer, a carbon black reinforcing agent having a STSA specific surface area of from 0 to 200 m7g, and a til silane coupling agent in an amount depending on the amount of carbon black.
- the organosilane coupling agent has the following formula:
- A is -SCN, -SH, -CI, -NH 2 ;
- R and R' are a branched or linear alkyl or phenol group having from 1 to 4 carbon atoms, and R and R' may be the same or different;
- n 0, 1 or 2;
- Alk is a linear or branched hydrocarbon group having 1 to 1 carbon atom
- Alkenyl is a linear or branched alkenyl group containing from 1 to 1 carbon atom
- n 0 or 1
- Ar is an aryl group having 6 to 12 carbon atoms
- p is 0 or 1, p and n cannot be 0 at the same time;
- x is 2 to 8;
- the most commonly used ones are bis(triethoxypropylsilane) tetrasulfide and disulfide, 3-thiocyanopropyl-triethoxysilane, ⁇ -mercapto-trimethoxysilane.
- the amount of the organosilane is changed according to the amount of the carbon black.
- the test results show that the amount of the organosilane coupling agent is 0.5% by weight of the amount of the carbon black (the range of kt% is preferred).
- a rubber composition having low hysteresis loss and high abrasion resistance comprising: (A) 100 parts by weight of rubber;
- the rubber is mixed with carbon black and an organosilane coupling agent, and the kneading temperature is in the range of 130-16 CTC for at least 1-5 minutes;
- the carbon black masterbatch, the antioxidant, the active agent, the accelerator, and the chemical agent are kneaded in a ratio of the composition to prepare a rubber composition, and the final rubber mixing process is one or more segments;
- the rubber comprises one or more of natural rubber, synthetic polyisoprene rubber, cis-butyl rubber, styrene-butadiene rubber, and other diene-containing unit-containing polymers;
- R and R' are a branched or linear alkyl or phenol group having from 1 to 4 carbon atoms, and R and R' may be the same or different;
- n 0, 1 or 2;
- Alk is a linear or branched hydrocarbon group having 1 to 1 carbon atom
- Alk ⁇ l is a linear or branched alkenyl group having 1 to 1 carbon atom
- n 0 or 1
- Ar is an aryl group having 6 to 12 carbon atoms
- p is 0 or 1, p and n cannot be 0 at the same time;
- X is 2 to 8;
- the most commonly used ones are bis(triethoxypropylsilane) tetrasulfide and disulfide, 3-thiocyanopropyl-triethoxysilane, gamma-mercapto-trimethoxysilane;
- the rubber composition wherein the silicone compound coupling agent is used in an amount of 0.5% by weight to 10% by weight, preferably 1% by weight to 8%, more preferably 2% by weight to 5% by weight based on the amount of the carbon black;
- the activator is one or more of a metal oxide and a fatty acid combination and a fatty acid metal soap salt, and the metal oxide is one or more of zinc oxide, magnesium oxide, etc., and the fatty acid metal soap salt is One or more of zinc stearate, zinc borate, etc.;
- the antioxidant includes an amine antioxidant, a quinoline anti-aging agent, a benzimidazole anti-aging agent, a physical protective wax;
- the accelerator includes, but is not limited to,
- the method for measuring the binding rubber content of the 3 ⁇ 4 ⁇ 4t adhesive composition of the present invention is as follows: Weighing a certain weight of unvulcanized rubber sample Soak the unvulcanized rubber in the organic solvent (the preferred toluene solution) for 3 days; remove the sample, replace the immersion: permeable, and then immerse the sample in the organic solution for three days; then wash the sample dry and dry the amount. Calculate the bound gum content according to the theoretical calculation formula.
- Isoprene rubber IR Qingdao Ikos Materials Co., Ltd.;
- Liquid silicone firing coupling agent SG-SI998 (bis(triethoxypropylsilane) tetrasulfide), Nanjing Shuguang Auxiliary Co., Ltd.;
- Organosilane coupling agent X50S Contains 50% N330 carbon black, 50% bis(triethoxypropylsilane) tetraide, Evonik Iridium (Rizhao) Chemical Industry Co., Ltd.;
- Zinc oxide Dalian zinc oxide plant
- Antioxidant 020 N-(1.3-dimethylbutyl)- ⁇ '-phenyl-p-phenylenediamine, Jiangsu Shengao Chemical Technology Co., Ltd.; Anti-aging agent RD: 2,2,4-trimethyl-1, 2-dihydroquinoline polymer, Tianjin Kemai Auxiliary Co., Ltd.; accelerator NS ( ⁇ -tert-butyl-2-benzothiazole sulfenamide): Shandong Shanghao Chemical Co., Ltd.; sulfur: Linyi Luozhuang Xin'an Chemical plant Manual comparison example 1
- One part of the mixture was filled into 100 parts by weight of 20# standard rubber in an internal mixer with a rotation speed of 90 rpm. After 60 seconds of mastication, 33 parts by weight of carbon black N234 was added to the top plug; after 90 seconds of mixing, the top plug was cleaned and added. 17 parts by weight of carbon black; after mixing for 30 seconds, adding 5 parts by weight of zinc oxide, 3 parts by weight of stearic acid, 1.5 parts by weight of antioxidant RD, 1.5 parts by weight of 145 antioxidant 4020, 1 part by weight of microcrystalline wax, mixing 30 After the second, the top plug is cleaned, and the masterbatch is discharged for 30 seconds. The mixing time is 240 seconds, and the rubber discharge is 158 °C.
- the final rubber compound is mixed with 162 parts by weight of a mixed masterbatch in an internal mixer of 60 ⁇ , and after 30 seconds of mixing, the top plug is added with 1 part by weight of 5 yellow, 1.2 parts by weight of ⁇ agent NS, and mixed. After 60 seconds of refining, it is cleaned for 30 seconds and then discharged into the final rubber. The mixing time is 120 seconds. Discharge 3 ⁇ 4t3 ⁇ 4 98°C
- the basic formula other compounding agent is: SMR20 100; N23450; zinc oxide 5; stearic acid 3; antioxidant 4020 1. 5; antioxidant RD 1. 5, liquid silicon germanium coupling agent SG-SI9884, microcrystalline wax 1; Promoter NS 1. 2; sulfur yellow 1.
- One part of the mixture is filled with 100 parts by weight of 20# standard rubber in a mixer with a speed of 9 (3 ⁇ 4 pm), and after 60 seconds of mastication, a top plug is added to add 33 parts by weight of carbon black N234; after 90 seconds of mixing, i ⁇ h Top plug cleaning, adding 17 parts by weight of carbon black; 155 mixing for 30 seconds, adding 4 parts by weight of liquid silicon, 5 parts by weight of zinc oxide, 3 parts by weight of stearic acid, 1.5 parts by weight of antioxidant RD, 1.5 parts by weight of antioxidant 020, 1 part by weight of microcrystalline wax, after mixing for 30 seconds, ⁇ strong top plug is cleaned, and then mixed for 30 seconds to discharge the masterbatch.
- the mixing time is 240 seconds, and the discharge temperature is 154 °C.
- the final rubber is filled with 166 parts by weight of a masterbatch in an internal mixer with a key of 60 rpm. After mixing for 30 seconds, i ⁇ h top plug is added with 1 part by weight of sulfur, 1.2 parts by weight of fiber NS, and kneading 60. After the second cleaning, after mixing for 30 seconds, the final 160 rubber is discharged, the mixing time is 120 seconds, and the rubber discharge is 3 ⁇ 43 ⁇ 4 is 102 °C.
- Example 1 the performance of Example 1 in which a silane coupling agent was added was compared with that of Comparative Example 1, and the content of the bonding gum was increased by 20%; the resilience performance at 23 ° C and 60 ° C was increased by 11% or more. The temperature rise at the bottom of the compressed heat is reduced by 12%. Abrasive performance improvements are particularly noticeable, DIN wear performance is increased by 18%; Akron wear index is increased by 13%. .
- a mixing process 100 parts by weight of SMR20 is added to an internal mixer at a speed of 90 rpm, and after 60 seconds of mastication, 26 parts by weight of N115 is added to the top plug; after 90 seconds of mixing, the top plug is cleaned, and the remaining 14 parts by weight of no N115 is added.
- Final rubber mixing process Add 160 weights to the mixer at 60 rpm! ⁇ One-stage mixing of the masterbatch, after 30 seconds of mastication, adding 1 part by weight of sulfur and 1.2 parts by weight of accelerator NS; mixing after 60 seconds of mixing; mixing after 175 minutes of smelting for 30 seconds, the total mixing time is 120 In seconds, the discharge temperature is 95 °C.
- the load is 149! ⁇ divided into a batch of masterbatch, kneaded for 80 seconds to put on the top plug, force 5 parts by weight of zinc oxide, 3 parts by weight of stearic acid, 1.5 parts by weight of antioxidant RD, 1.5 parts by weight of anti-aging agent bar; mixing 70 seconds cleaning ; further mixing for 30 seconds; the total mixing time is 180 seconds, and the glue is 3 ⁇ 43 ⁇ 4t at 155 °C.
- Example 2 As can be seen from the comparative data of Table 4, the temperature rise of the compressed heat generating bottom of Example 2 was lower than that of Comparative Example 2.
- the dynamic viscoelastic spectrometer measures the tendency of the rubber composition to change in loss factor from low temperature to high temperature. It can be seen from Fig. 1 that the loss factor of Example 2 is lower than that of the Comparative Example 2 in the range of 50 ° C to 80 ° C, indicating that the rolling resistance is lower than that of Comparative Example 2, and it is applied to the tire to reduce the rolling resistance.
- Example 3 As can be seen from the comparative data of Table 5, the compression heat generation of Example 3 was 8% lower than that of Comparative Example 3, the elasticity was improved, and the binder content was increased by 5%, using the rubber composition and process method designed by the present invention. It is indicated that the use of the method of the present invention can improve the combination of carbon black and rubber, thereby improving dynamic performance and reducing wear.
- a masterbatch 150 parts by weight of a masterbatch is added, and the top plug is kneaded for 80 seconds, and 5 parts by weight of zinc oxide, 3 parts by weight of stearic acid, and 1.5 parts by weight of an antioxidant are applied.
- RD 1.5 parts by weight of anti-aging agent bar, micro 245 crystal wax 1, mixing for 70 seconds to clean; re-kneading for 30 seconds to discharge; total mixing time is 180 seconds.
- the glue is 151 °C.
- the mixer 61 of the car 61 is 60 rpm, 162 parts by weight of the two-stage mixing masterbatch, mixing for 30 seconds to put the top plug plus 1.5 parts by weight of sulfur and 1.8 parts by weight of the fiber NS; mixing 60 seconds cleaning Re-kneading for 30 seconds, the total mixing time is 120 seconds, and the glue is 98 °C.
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Abstract
La présente invention porte sur une composition de caoutchouc et son procédé de préparation. La composition de caoutchouc comprend : 100 parties en poids d'un caoutchouc, 5-120 parties en poids de noir de carbone, 0,5-12 parties en poids d'un agent de couplage organosilane, et un certain nombre de parties en poids d'un activateur, d'un agent anti-vieillissement, de soufre et d'un accélérateur de vulcanisation. Les étapes du procédé de préparation d'une telle composition de caoutchouc comprennent : le mélange du caoutchouc, du noir de carbone et de l'agent de couplage organosilane en un mélange maître sous une certaine condition de mélange, puis l'addition d'un ou de plusieurs auxiliaires de caoutchouc pour former la composition de caoutchouc. La présente invention peut être utilisée dans des pneumatiques pour améliorer la résistance à l'abrasion et réduire la résistance au roulement.
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CN201410031736.5A CN103897225A (zh) | 2014-01-23 | 2014-01-23 | 一种含有机硅烷偶联剂及炭黑的橡胶组合物及其制备方法 |
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CN104311929A (zh) * | 2014-11-03 | 2015-01-28 | 怡维怡橡胶研究院有限公司 | 一种连续式制备的橡胶母炼胶在轿车胎胎面胶中的应用 |
CN106589482A (zh) * | 2016-12-24 | 2017-04-26 | 安徽佳通乘用子午线轮胎有限公司 | 一种改进硫化体系的橡胶及其制备方法和应用 |
DE102017221232A1 (de) * | 2017-11-28 | 2019-05-29 | Continental Reifen Deutschland Gmbh | Schwefelvernetzbare Kautschukmischung, Vulkanisat der Kautschukmischung und Fahrzeugreifen |
CN112280112A (zh) * | 2020-10-21 | 2021-01-29 | 安徽佳通乘用子午线轮胎有限公司 | 一种降低滚动阻力的胎面橡胶组合物及其制备方法 |
CN113861526B (zh) * | 2021-09-07 | 2022-10-14 | 北京化工大学 | 一种高耐磨低生热炭黑母胶及其制备方法 |
CN114316635A (zh) * | 2021-12-30 | 2022-04-12 | 宁波德泰化学有限公司 | 一种双亲炭黑及其制备方法 |
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EP1260544A1 (fr) * | 2001-05-24 | 2002-11-27 | Sumitomo Rubber Industries Ltd. | Compostion de caoutchouc pour bande de roulement de pneu et pneu utlisant celle-ci |
CN101096433A (zh) * | 2006-06-30 | 2008-01-02 | 住友橡胶工业株式会社 | 顶胎面用橡胶组合物及具有该顶胎面的充气轮胎 |
CN101190978A (zh) * | 2006-12-01 | 2008-06-04 | 横滨橡胶株式会社 | 用于轮胎的橡胶组合物的制备方法 |
WO2008123306A1 (fr) * | 2007-03-27 | 2008-10-16 | Bridgestone Corporation | Procédé de fabrication d'une composition de caoutchouc pour une bande de roulement de pneumatique |
CN101469035A (zh) * | 2007-12-25 | 2009-07-01 | 双钱集团(如皋)轮胎有限公司 | 一种生胶原材料复配混炼工艺 |
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CN102604167B (zh) * | 2012-01-19 | 2013-09-11 | 宁波兴柯汽车新材料科技有限公司 | 一种硫化橡胶的制备方法 |
CN102604170A (zh) * | 2012-03-07 | 2012-07-25 | 安徽大瑞橡胶有限公司 | 一种轮胎胎冠胶料及其混炼方法 |
CN102898692B (zh) * | 2012-11-02 | 2015-02-11 | 北京化工大学 | 一种胎肩垫胶复合材料及其制备方法 |
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- 2014-01-23 CN CN201710115973.3A patent/CN106916345A/zh active Pending
- 2014-01-23 CN CN201410031736.5A patent/CN103897225A/zh active Pending
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EP1260544A1 (fr) * | 2001-05-24 | 2002-11-27 | Sumitomo Rubber Industries Ltd. | Compostion de caoutchouc pour bande de roulement de pneu et pneu utlisant celle-ci |
CN101096433A (zh) * | 2006-06-30 | 2008-01-02 | 住友橡胶工业株式会社 | 顶胎面用橡胶组合物及具有该顶胎面的充气轮胎 |
CN101190978A (zh) * | 2006-12-01 | 2008-06-04 | 横滨橡胶株式会社 | 用于轮胎的橡胶组合物的制备方法 |
WO2008123306A1 (fr) * | 2007-03-27 | 2008-10-16 | Bridgestone Corporation | Procédé de fabrication d'une composition de caoutchouc pour une bande de roulement de pneumatique |
CN101469035A (zh) * | 2007-12-25 | 2009-07-01 | 双钱集团(如皋)轮胎有限公司 | 一种生胶原材料复配混炼工艺 |
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