CN114805959B - Pre-dispersed rubber auxiliary master batch, preparation method and application thereof - Google Patents
Pre-dispersed rubber auxiliary master batch, preparation method and application thereof Download PDFInfo
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- CN114805959B CN114805959B CN202210465531.2A CN202210465531A CN114805959B CN 114805959 B CN114805959 B CN 114805959B CN 202210465531 A CN202210465531 A CN 202210465531A CN 114805959 B CN114805959 B CN 114805959B
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 92
- 239000005060 rubber Substances 0.000 title claims abstract description 92
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229920001577 copolymer Polymers 0.000 claims abstract description 68
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 239000004636 vulcanized rubber Substances 0.000 claims abstract description 21
- 239000010692 aromatic oil Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 83
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 35
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- 241001441571 Hiodontidae Species 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 25
- 238000001125 extrusion Methods 0.000 claims description 21
- 238000005469 granulation Methods 0.000 claims description 21
- 230000003179 granulation Effects 0.000 claims description 21
- 239000011787 zinc oxide Substances 0.000 claims description 17
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 16
- 239000005062 Polybutadiene Substances 0.000 claims description 12
- 229920002857 polybutadiene Polymers 0.000 claims description 12
- 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 11
- 230000003712 anti-aging effect Effects 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- UEZWYKZHXASYJN-UHFFFAOYSA-N cyclohexylthiophthalimide Chemical group O=C1C2=CC=CC=C2C(=O)N1SC1CCCCC1 UEZWYKZHXASYJN-UHFFFAOYSA-N 0.000 claims description 8
- 244000043261 Hevea brasiliensis Species 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 7
- 229920003052 natural elastomer Polymers 0.000 claims description 7
- 229920001194 natural rubber Polymers 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 4
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 4
- 229960002447 thiram Drugs 0.000 claims description 4
- MIIBUHIQXLFJFP-UHFFFAOYSA-N 3-methyl-1-[[3-[(3-methyl-2,5-dioxopyrrol-1-yl)methyl]phenyl]methyl]pyrrole-2,5-dione Chemical group O=C1C(C)=CC(=O)N1CC1=CC=CC(CN2C(C(C)=CC2=O)=O)=C1 MIIBUHIQXLFJFP-UHFFFAOYSA-N 0.000 claims description 3
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims 2
- 230000001070 adhesive effect Effects 0.000 claims 2
- 238000004073 vulcanization Methods 0.000 abstract description 10
- 238000007906 compression Methods 0.000 abstract description 8
- 230000006835 compression Effects 0.000 abstract description 8
- 230000020169 heat generation Effects 0.000 abstract description 7
- 239000004014 plasticizer Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 5
- 238000005096 rolling process Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229920003049 isoprene rubber Polymers 0.000 description 18
- 239000000203 mixture Substances 0.000 description 15
- 238000009472 formulation Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 8
- 239000000956 alloy Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 229920005549 butyl rubber Polymers 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- NSYRAUUZGRPOHS-BQYQJAHWSA-N (3E)-2-methylocta-1,3-diene Chemical compound CCCC\C=C\C(C)=C NSYRAUUZGRPOHS-BQYQJAHWSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920002943 EPDM rubber Polymers 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000004596 additive masterbatch Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003348 petrochemical agent Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- -1 accelerator Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2307/00—Characterised by the use of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2409/00—Characterised by the use 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
- C08K3/02—Elements
- C08K3/06—Sulfur
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
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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 relates to the technical field of rubber synthesis and application, in particular to a pre-dispersed rubber auxiliary agent master batch, a preparation method and application thereof. The pre-dispersed rubber auxiliary master batch is prepared from raw materials comprising a low-Mooney trans-1, 4-diene copolymer and a rubber auxiliary; the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the rubber auxiliary agent is 20-50: 50-80. The pre-dispersed rubber auxiliary master batch contains the reactive plasticizer low-Mooney trans-1, 4-diene copolymer, so that the rubber auxiliary can be more uniformly dispersed in a formula system and participate in a crosslinking reaction during vulcanization, and meanwhile, the introduction of the low-Mooney trans-1, 4-diene copolymer can reduce the use of non-reactive plasticizer environment-friendly aromatic oil in the formula system, so that the performance of preparing vulcanized rubber is obviously better. The vulcanized rubber prepared from the pre-dispersed rubber auxiliary agent master batch has lower rolling resistance and compression heat generation, and simultaneously has better wear resistance.
Description
Technical Field
The invention relates to the technical field of rubber synthesis and application, in particular to a pre-dispersed rubber auxiliary agent master batch, a preparation method and application thereof.
Background
The traditional rubber auxiliary agents (such as accelerator, sulfur, zinc oxide and the like) are powder, and have more defects in providing special physical properties for rubber products, firstly, dust is generated in the use process, so that inaccurate metering is caused, and the occupational health of operators is influenced; secondly, the dispersion effect of the powder rubber auxiliary agent in the rubber matrix is relatively poor, and the physical and mechanical properties of the rubber product cannot be well exerted.
The pre-dispersion rubber additive master batch technology prepares the common powdery rubber additive, the carrier, the modifier and the processing additive into the granular rubber additive in advance, can well solve the problem of dust pollution, and is beneficial to clean production of rubber product companies. The selection of the carrier is critical, and more carriers such as ethylene propylene diene monomer rubber/ethylene-vinyl acetate copolymer rubber (EPDM/EVA), butadiene Rubber (BR), nitrile Butadiene Rubber (NBR) and the like are reported in 2013 in the current market. The EPDM/EVA system is used as a rubber auxiliary carrier, and has good quality stability in the storage process due to low unsaturated bond content, but is difficult to participate in the crosslinking reaction under a sulfur vulcanization system; the BR, NBR and other saturated bonds have high content, and the quality stability in the storage process is relatively poor.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a pre-dispersed rubber auxiliary agent master batch, a preparation method and application thereof, and the vulcanized rubber prepared from the pre-dispersed rubber auxiliary agent master batch has lower rolling resistance and compression heat generation and better wear resistance.
The invention provides a pre-dispersed rubber auxiliary master batch, which is prepared from raw materials including a low-Mooney trans-1, 4-diene copolymer and a rubber auxiliary;
the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the rubber auxiliary agent is 20-50: 50-80.
Preferably, the low mooney trans-1, 4-diene copolymer has a mooney viscosity of 5 to 30.
Preferably, the low-Mooney trans-1, 4-diene copolymer comprises low-Mooney trans-butyl-isoprene rubber or a low-Mooney trans-isoprene rubber in-kettle alloy.
Preferably, the alloy in the low-Mooney trans-isoprene rubber kettle is obtained by reacting low-Mooney trans-butyl-isoprene rubber with low-Mooney trans-isoprene rubber;
in the preparation raw materials of the alloy in the low-Mooney trans-isoprene rubber kettle, the mass ratio of the low-Mooney trans-butadiene-isoprene rubber to the low-Mooney trans-isoprene rubber is 15-25: 75-85.
Preferably, in the low-Mooney trans-butadiene-isoprene rubber, the molar content of butadiene structural units is less than or equal to 20% or more than or equal to 70%.
Preferably, the rubber auxiliary agent comprises zinc oxide, an accelerator, a vulcanizing agent, a scorch retarder or an anti-reversion agent;
the accelerator comprises at least one of N-tertiary butyl-2-benzothiazole sulfenamide, N-cyclohexyl-2-benzothiazole sulfenamide, dibenzothiazyl disulfide and tetramethylthiuram disulfide;
the vulcanizing agent is selected from sulfur;
the scorch retarder is selected from N-cyclohexyl thio phthalimide;
the anti-reversion agent is selected from 1, 3-bis (citraconimidomethyl) benzene.
The invention also provides a preparation method of the pre-dispersed rubber auxiliary master batch, which comprises the following steps:
and (3) carrying out banburying blending, extrusion granulation on the low-Mooney trans-1, 4-diene copolymer and the rubber auxiliary agent to obtain the pre-dispersed rubber auxiliary agent master batch.
Preferably, the banburying and blending temperature is 55-65 ℃, the rotating speed is 45-55 rpm, and the time is 5-10 min;
the temperature of the extrusion granulation is 65-75 ℃ and the rotating speed is 15-25 rpm.
The invention also provides vulcanized rubber which is prepared from the following raw materials in parts by weight:
the auxiliary master batch comprises the pre-dispersed rubber auxiliary master batch or the pre-dispersed rubber auxiliary master batch prepared by the preparation method.
Preferably, the auxiliary agent master batch comprises a substance a, a substance b, a substance c and a substance d;
15-25 parts of a substance a;
the weight part of the substance b is 1-3 parts;
the weight part of the substance c is 1-3 parts;
the weight part of the substance d is 0.2-0.3 part;
the substance a is prepared from raw materials comprising low-Mooney trans-1, 4-diene copolymer and zinc oxide; in the substance a, the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the zinc oxide is 20-50: 50-80 parts;
the substance b is prepared from raw materials comprising a low-Mooney trans-1, 4-diene copolymer and an accelerator; in the substance b, the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the accelerator is 20-50: 50-80 parts;
the substance c is prepared from raw materials comprising a low-Mooney trans-1, 4-diene copolymer and a vulcanizing agent; in the substance c, the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the vulcanizing agent is 20-50: 50-80 parts;
the substance d is prepared from raw materials comprising a low-Mooney trans-1, 4-diene copolymer and a scorch retarder; in the substance d, the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the scorch retarder is 20-50: 50-80.
The invention provides a pre-dispersed rubber auxiliary master batch, which is prepared from raw materials including a low-Mooney trans-1, 4-diene copolymer and a rubber auxiliary; the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the rubber auxiliary agent is 20-50: 50-80. The pre-dispersed rubber auxiliary master batch prepared by the invention contains the reactive plasticizer low-Mooney trans-1, 4-diene copolymer, can promote the rubber auxiliary to be more uniformly dispersed under a formula system and participate in a crosslinking reaction during vulcanization, and meanwhile, the introduction of the low-Mooney trans-1, 4-diene copolymer can reduce the use of non-reactive plasticizer environment-friendly aromatic hydrocarbon oil under the formula system, so that the performance of preparing vulcanized rubber is obviously better. The vulcanized rubber prepared from the pre-dispersed rubber auxiliary agent master batch has lower rolling resistance and compression heat generation, and simultaneously has better wear resistance.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a pre-dispersed rubber auxiliary master batch, which is prepared from raw materials including a low-Mooney trans-1, 4-diene copolymer and a rubber auxiliary;
the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the rubber auxiliary agent is 20-50: 50-80.
In certain embodiments of the present invention, the low mooney trans-1, 4-diene copolymer and rubber auxiliary are present in a mass ratio of 50: 50. 20:80 or 40:60.
in certain embodiments of the present invention, the low mooney trans-1, 4-diene copolymer has a mooney viscosity of from 5 to 30.
In certain embodiments of the invention, the low mooney trans-1, 4-diene copolymer comprises low mooney trans-butyl-isoprene rubber or a low mooney trans-isoprene rubber in-pot alloy.
In certain embodiments of the present invention, the low mooney trans-butyl rubber has a mooney viscosity of from 5 to 30. In certain embodiments, the low mooney trans-butyl rubber has a mooney viscosity of 30, 5, 15, or 10. In certain embodiments of the present invention, the low Mooney trans-butyl rubber has a molar content of butadiene structural units of 20% or more or equal to 70% or more. In certain embodiments, the low mooney trans-butyl rubber has a molar content of butadiene structural units of 20%, 5%, 75%, or 95%.
In certain embodiments of the invention, the low mooney trans-butyl rubber is derived from shandong hua polymeric materials limited.
In certain embodiments of the present invention, the low Mooney trans isoprene rubber in-kettle alloy is derived from the reaction of low Mooney trans butyl isoprene rubber and low Mooney trans isoprene rubber. In certain embodiments of the invention, the low mooney trans isoprene rubber in-kettle alloy is derived from eastern polymeric materials inc.
In some embodiments of the present invention, in the preparation raw materials of the alloy in the low-mooney trans-isoprene rubber kettle, the mass ratio of the low-mooney trans-butadiene-isoprene rubber to the low-mooney trans-isoprene rubber is 15-25: 75-85.
In certain embodiments of the present invention, the rubber auxiliary comprises zinc oxide, accelerators, vulcanizing agents, scorch retarders, or reversion retarders.
In certain embodiments of the present invention, the accelerator comprises at least one of N-tert-butyl-2-benzothiazole sulfenamide (NS), N-cyclohexyl-2-benzothiazole sulfenamide (CBS), dibenzothiazyl Disulfide (DM), and tetramethylthiuram disulfide (TMTD).
In certain embodiments of the invention, the vulcanizing agent is selected from sulfur.
In certain embodiments of the present invention, the scorch retarder is selected from N-cyclohexylthio-phthalimide (CTP).
In certain embodiments of the invention, the anti-reversion agent is selected from 1, 3-bis (citraconimidomethyl) benzene (WK 901).
The invention also provides a preparation method of the pre-dispersed rubber auxiliary master batch, which comprises the following steps:
and (3) carrying out banburying blending, extrusion granulation on the low-Mooney trans-1, 4-diene copolymer and the rubber auxiliary agent to obtain the pre-dispersed rubber auxiliary agent master batch.
In certain embodiments of the invention, the internal mixing temperature is 55 to 65 ℃, the rotation speed is 45 to 55rpm, and the time is 5 to 10 minutes. In certain embodiments of the invention, the internal blend is at a temperature of 60℃and a rotational speed of 50rpm for a period of 5 minutes.
In certain embodiments of the invention, the extrusion granulation temperature is 65 to 75℃and the rotational speed is 15 to 25rpm. In certain embodiments of the invention, the extrusion granulation temperature is 70℃and the rotational speed is 20rpm.
In the invention, the preparation of the pre-dispersed rubber auxiliary master batch needs two processes of banburying, blending, extrusion and granulation; the internal mixing and granulating can be carried out by adopting an internal mixer and a screw extruder for extrusion and granulation, and the internal mixing and granulating of the low-Mooney trans-1, 4-diene copolymer and the rubber auxiliary agent can be simultaneously realized by adopting one screw extruder.
The invention also provides vulcanized rubber which is prepared from the following raw materials in parts by weight:
the auxiliary master batch comprises the pre-dispersed rubber auxiliary master batch or the pre-dispersed rubber auxiliary master batch prepared by the preparation method.
In some embodiments of the present invention, the auxiliary master batch includes a substance a, a substance b, a substance c and a substance d, and specifically, the vulcanized rubber is prepared from the following raw materials in parts by weight:
the substance a is prepared from raw materials comprising low-Mooney trans-1, 4-diene copolymer and zinc oxide; in the substance a, the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the zinc oxide is 20-50: 50-80 parts;
the substance b is prepared from raw materials comprising a low-Mooney trans-1, 4-diene copolymer and an accelerator; in the substance b, the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the accelerator is 20-50: 50-80 parts;
the substance c is prepared from raw materials comprising a low-Mooney trans-1, 4-diene copolymer and a vulcanizing agent; in the substance c, the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the vulcanizing agent is 20-50: 50-80 parts;
the substance d is prepared from raw materials comprising a low-Mooney trans-1, 4-diene copolymer and a scorch retarder; in the substance d, the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the scorch retarder is 20-50: 50-80.
In the vulcanized rubber, the components and the properties of the low-Mooney trans-1, 4-diene copolymer are the same as those of the vulcanized rubber, and the details are not repeated here.
In certain embodiments of the invention, the natural rubber is 80 parts by weight. In certain embodiments of the invention, the natural rubber is identified as SCRWF, produced by the sea chest group.
In certain embodiments of the present invention, the butadiene rubber is 20 parts by weight. In certain embodiments of the present invention, the butadiene rubber is identified as BR 9000, manufactured by Qilu rubber division.
In certain embodiments of the invention, the parts by weight of the substance a is 10 parts.
In the present invention, the substance a is prepared from a raw material comprising a low mooney trans-1, 4-diene copolymer and zinc oxide.
In certain embodiments of the invention, the mass ratio of low mooney trans-1, 4-diene copolymer to zinc oxide in substance a is 40:60 or 20:80.
in the invention, the preparation method of the substance a is the same as the preparation method of the pre-dispersed rubber auxiliary master batch. In certain embodiments of the invention, substance a is prepared according to the following method:
and (3) carrying out banburying blending, extrusion granulation on the low-Mooney trans-1, 4-diene copolymer and zinc oxide to obtain a substance a.
In certain embodiments of the invention, the internal mixing temperature is 60 ℃, the rotation speed is 50rpm, and the time is 5min;
in certain embodiments of the invention, the extrusion granulation temperature is 70℃and the rotational speed is 20rpm.
In certain embodiments of the present invention, the stearic acid is present in an amount of 2 parts by weight.
In certain embodiments of the present invention, the anti-aging agent is 3 parts by weight. In certain embodiments of the present invention, the anti-aging agent comprises N- (1, 3-dimethyl) butyl-N' -phenyl-p-phenylenediamine (anti-aging agent 4020) and a2, 4-trimethyl-1, 2-dihydroquinoline polymer (anti-aging agent RD), the anti-aging agent 4020 and the anti-aging agent RD having a mass ratio of 2:1.
in certain embodiments of the present invention, the carbon black is present in an amount of 50 parts by weight. In certain embodiments of the present invention, the carbon black is selected from carbon black N220.
In certain embodiments of the invention, the aromatic oil is 6 parts or 2 parts by weight. In certain embodiments of the present invention, the aromatic oil is selected from VIVATEC 500 manufactured by hansheng petrochemicals (Ningbo) limited.
In certain embodiments of the invention, the parts by weight of the substance b is 2 parts.
In the present invention, the substance b is prepared from a raw material comprising a low mooney trans-1, 4-diene copolymer and an accelerator. In certain embodiments of the invention, the accelerator is NS.
In certain embodiments of the invention, the mass ratio of low mooney trans-1, 4-diene copolymer to accelerator in substance b is 50:50 or 20:80.
in the present invention, the preparation method of the substance b is the same as the preparation method of the pre-dispersed rubber auxiliary master batch described above. In certain embodiments of the invention, substance b is prepared according to the following method:
and (3) carrying out banburying blending, extrusion granulation on the low-Mooney trans-1, 4-diene copolymer and the accelerator to obtain a substance b.
In certain embodiments of the invention, the internal mixing temperature is 60 ℃, the rotation speed is 50rpm, and the time is 5min;
in certain embodiments of the invention, the extrusion granulation temperature is 70℃and the rotational speed is 20rpm.
In certain embodiments of the invention, the parts by weight of substance c is 2 parts.
In the present invention, the substance c is prepared from a raw material comprising a low mooney trans-1, 4-diene copolymer and a vulcanizing agent.
In certain embodiments of the present invention, the mass ratio of low mooney trans-1, 4-diene copolymer to vulcanizing agent in substance c is 50:50 or 20:80.
in the present invention, the preparation method of the substance c is the same as the preparation method of the pre-dispersed rubber auxiliary master batch described above. In certain embodiments of the invention, substance c is prepared according to the following method:
and (3) carrying out banburying blending, extrusion granulation on the low-Mooney trans-1, 4-diene copolymer and the vulcanizing agent to obtain a substance c.
In certain embodiments of the invention, the internal mixing temperature is 60 ℃, the rotation speed is 50rpm, and the time is 5min;
in certain embodiments of the invention, the extrusion granulation temperature is 70℃and the rotational speed is 20rpm.
In certain embodiments of the invention, the parts by weight of substance d is 0.25 parts.
In the present invention, the substance d is prepared from a raw material comprising a low mooney trans-1, 4-diene copolymer and a scorch retarder. In certain embodiments of the present invention, the scorch retarder is CTP.
In certain embodiments of the invention, the mass ratio of low mooney trans-1, 4-diene copolymer to scorch retarder in substance d is 20:80.
in the invention, the preparation method of the substance d is the same as the preparation method of the pre-dispersed rubber auxiliary master batch. In certain embodiments of the invention, substance d is prepared according to the following method:
and (3) carrying out banburying blending, extrusion granulation on the low-Mooney trans-1, 4-diene copolymer and the scorch retarder to obtain a substance d.
In certain embodiments of the invention, the internal mixing temperature is 60 ℃, the rotation speed is 50rpm, and the time is 5min;
in certain embodiments of the invention, the extrusion granulation temperature is 70℃and the rotational speed is 20rpm.
The invention also provides a preparation method of the vulcanized rubber, which comprises the following steps:
a) Mixing natural rubber and butadiene rubber, banburying for 0.5-1.5 min, mixing with a substance a, stearic acid, an anti-aging agent, carbon black and aromatic oil, and continuing banburying to obtain a section of banburying;
b) Mixing the first-stage banburying glue, the substance b, the substance c and the substance d, and banburying to obtain a second-stage banburying glue;
c) And vulcanizing the two-stage rubber compound to obtain vulcanized rubber.
In the preparation method of the vulcanized rubber, the adopted raw material components are as follows
In step A):
in certain embodiments of the invention, the temperature of the banburying is 65-75 ℃. In certain embodiments, the temperature of the banburying is 70 ℃.
In certain embodiments of the invention, the speed of the banburying is 60-80 r/min. In certain embodiments, the speed of the banburying is 70r/min.
In certain embodiments of the invention, the time for the banburying is 1min.
In certain embodiments of the invention, the temperature of the continuous banburying is 65-75 ℃. In certain embodiments, the temperature at which the banburying continues is 70 ℃.
In some embodiments of the invention, the speed of the continuous banburying is 60-80 r/min. In some embodiments, the speed of the continuous banburying is 70r/min.
In certain embodiments of the invention, the time to continue the banburying is 3 to 5 minutes. In certain embodiments, the time to continue the banburying is 3 minutes.
In some embodiments of the present invention, after the continuous banburying is completed, the method further includes: cleaning an upper top bolt of the internal mixer, discharging glue and then discharging a lower sheet.
In some embodiments of the invention, after obtaining a section of the masterbatch, further comprising: standing at room temperature. In certain embodiments, the room temperature dwell time is 2 hours.
In step B):
in certain embodiments of the invention, the temperature of the banburying is 45-55 ℃. In certain embodiments, the temperature of the banburying is 50 ℃.
In certain embodiments of the invention, the speed of the banburying is 40-60 r/min. In certain embodiments, the speed of the banburying is 50r/min.
In certain embodiments of the invention, the banburying is for a period of 1 to 2 minutes. In certain embodiments, the time for the banburying is 1.5min.
In some embodiments of the present invention, after the banburying is completed, the method further comprises: and discharging glue and then discharging the glue.
In certain embodiments of the invention, after obtaining the two-stage masterbatch, further comprising: standing at room temperature. In certain embodiments, the room temperature dwell time is 1d.
In step C):
in certain embodiments of the invention, the temperature of the vulcanization is 140 to 160 ℃. In certain embodiments, the temperature of the vulcanization is 150 ℃.
In certain embodiments of the invention, the vulcanization pressure is 8 to 12MPa. In certain embodiments, the pressure of the vulcanization is 10MPa.
In certain embodiments of the invention, the vulcanization time is 10 to 20 minutes. In certain embodiments, the time of vulcanization is 15 minutes.
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
In the invention, when the low-Mooney trans-1, 4-diene copolymer is mixed with the powder rubber auxiliary agent, processing auxiliary agents such as a lubricant, a plasticizer and the like are not required to be added to improve the processing performance; the low Mooney trans-1, 4-diene copolymer can ensure that the pre-dispersed rubber auxiliary master batch is not adhered in the storage process on the premise of not using an anti-adhesion agent; the pre-dispersed rubber auxiliary agent master batch prepared by adopting the low-Mooney trans-1, 4-diene copolymer has good fluidity and good dispersing effect when used in a rubber formula; the low-Mooney trans-1, 4-diene copolymer can participate in vulcanization crosslinking reaction when being used in rubber products, and the prepared vulcanized rubber has more excellent application performance.
In order to further illustrate the present invention, the pre-dispersed rubber auxiliary master batch, the preparation method and the application thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
The raw materials used in the following examples are all generally commercially available.
In the examples, natural rubber is identified as SCRWF, produced by sea rubber group; the brand of butadiene rubber is BR 9000, which is produced by Qilu petrochemical rubber division; aromatic oils are selected from VIVATEC 500 manufactured by Hansen petrochemicals, inc.
Example 1
Preparation of pre-dispersed rubber auxiliary master batch:
the low-Mooney trans-butyl-pentan rubber (the molar content of the butadiene structural unit is 20 percent, the Mooney viscosity is 30 percent) and the accelerator N-tertiary butyl-2-benzothiazole sulfenamide (NS) are mixed according to the mass ratio of 50:50, putting the mixture into an internal mixer, and carrying out internal mixing for 5min at the rotating speed of the internal mixer: 50 revolutions per minute, initial temperature 60℃and then extrusion granulation in a twin screw extruder, screw temperature 70℃and speed 20rpm, produce substance b1 (NS-50 sample).
The mass ratio of the low-Mooney trans-butyl-pentan rubber to the accelerator N-tert-butyl-2-benzothiazole sulfenamide (NS) is replaced by 20:80, the remaining steps were carried out as described above to obtain substance b2 (NS-80 sample).
Example 2
Preparation of pre-dispersed rubber auxiliary master batch:
the low Mooney trans-butyl-pentyl rubber (butadiene structural unit molar content is 5 percent, mooney viscosity is 5) and zinc oxide (ZnO) are mixed according to the mass ratio of 40:60 is put into an internal mixer for banburying for 5min, and the rotation speed of the internal mixer is that: 50 revolutions per minute, initial temperature 60℃and then extrusion granulation in a twin screw extruder, screw temperature 70℃and rotational speed 20rpm, produced substance a1 (ZnO-60 sample).
Replacing the mass ratio of the low-Mooney trans-butyl-pentad rubber to zinc oxide with 20:80, and the rest steps were carried out according to the above steps to obtain a substance a2 (ZnO-80 sample).
Example 3
Preparation of pre-dispersed rubber auxiliary master batch:
the low Mooney trans-butyl-pentyl rubber (the molar content of the butadiene structural unit is 75 percent, the Mooney viscosity is 15) and sulfur powder (S) are mixed according to the mass ratio of 50:50, putting the mixture into an internal mixer, and carrying out internal mixing for 5min at the rotating speed of the internal mixer: 50 revolutions per minute, initial temperature 60℃and then extrusion granulation in a twin screw extruder, screw temperature 70℃and rotational speed 20rpm, produce substance c1 (S-50 sample).
Replacing the mass ratio of the low-Mooney trans-butyl-pentyl rubber to the sulfur powder with 20:80, and the rest steps are carried out according to the steps to obtain a substance c2 (S-80 sample).
Example 4
Preparation of pre-dispersed rubber auxiliary master batch:
the low Mooney trans-butyl-pentyl rubber (butadiene structural unit molar content is 95%, mooney viscosity is 10) and scorch retarder (CTP) are mixed according to the mass ratio of 20:80 is put into an internal mixer for banburying for 5min, and the rotation speed of the internal mixer is that: 50 revolutions per minute, initial temperature 60 ℃, then extrusion granulation in a twin screw extruder, screw temperature 70 ℃, rotational speed 20rpm, produced substance d (CTP-80 sample).
Example 5
A mix was prepared according to the formulation of table 1:
1) Mixing natural rubber and butadiene rubber, banburying for 1min, mixing with a substance a1 (or zinc oxide or ZnO-80), stearic acid, an anti-aging agent, carbon black and aromatic hydrocarbon oil, continuously banburying for 3min, cleaning an upper top bolt of an internal mixer, discharging rubber for 5min, and then discharging by an open mill to obtain a section of banburying; standing at room temperature for 2h;
2) Mixing the first-stage banburying compound, a substance b2 (or an accelerator), a substance c2 (or sulfur or S-80) and a substance d (or a scorch retarder or CTP-80), and banburying for 1.5min to obtain a second-stage banburying compound; standing at room temperature for 1d;
c) And vulcanizing the two-stage rubber compound at 150 ℃ and 10MPa for 15min to obtain vulcanized rubber.
Wherein, zinc oxide, an accelerator NS, sulfur and a scorch retarder CTP used in a comparison formula 1 are all in a powder state, a commercial pre-dispersed rubber auxiliary master batch is used in a comparison formula 2, and a novel pre-dispersed rubber auxiliary master batch prepared in the embodiment of the invention is used in an experimental formula.
Table 1 comparative and experimental formulations
| Sample of | Comparative formulation 1 | Comparative formulation 2 | Experimental formulation 1 | Experimental formulation 2 |
| Natural rubber | 80 | 80 | 80 | 80 |
| Butadiene rubber | 20 | 20 | 20 | 20 |
| Zinc oxide (powder) | 6.0 | 0 | 0 | 0 |
| ZnO-80 (commercially available) | 0 | 7.5 | 0 | 0 |
| ZnO-60 (prepared in example 2, a 1) | 0 | 0 | 10.0 | 10.0 |
| Stearic acid | 2.0 | 2.0 | 2.0 | 2.0 |
| Anti-aging agent | 3.0 | 3.0 | 3.0 | 3.0 |
| Carbon black N220 | 50.0 | 50.0 | 50.0 | 50.0 |
| Environment-friendly aromatic hydrocarbon oil | 6.0 | 6.0 | 6.0 | 2.0 |
| Accelerator NS (powder) | 1.6 | 0 | 0 | 0 |
| Accelerator NS-80 (commercially available) | 0 | 2.0 | 0 | 0 |
| Promoter NS-80 (actual)Example 1 preparation, b 2) | 0 | 0 | 2.0 | 2.0 |
| Sulfur (powder) | 1.6 | 0 | 0 | 0 |
| S-80 (commercially available) | 0 | 2.0 | 0 | 0 |
| S-80 (prepared in example 3, c 2) | 0 | 0 | 2.0 | 2.0 |
| Coke inhibitor CTP (powder) | 0.2 | 0 | 0 | 0 |
| CTP-80 (commercially available) | 0 | 0.25 | 0 | 0 |
| CTP-80 (prepared in example 4, d) | 0 | 0 | 0.25 | 0.25 |
The properties of the resulting vulcanizate were tested. The tensile strength of the vulcanizate was tested according to standard GB/T528-2009 using a Zwick/Roell 2005 electronic tensile tester from Zwick/Roell, germany. DIN abrasion performance was tested according to standard GB/T9867 with a MZ-4060 drum-type abrasion machine manufactured by Jiangsu Bright test machines Co., ltd., load weight: 10 + -0.2N. Test samples were tested for compression heat generation by using a GT-RH-2000 compression heat generation tester manufactured by Taiwan high-iron technologies Co., ltd under the following test conditions: the temperature is 55+/-1 ℃, the stroke is 4.45+/-0.03 mm, and the load is 1.00+/-0.03 MPa. 861 from Metrehler, switzerland e The dynamic thermo-mechanical performance analyzer tests tan delta value of vulcanized rubber at 60 ℃, frequency 10Hz and strain 5.0%. The results are shown in Table 2.
TABLE 2 results of Performance test of vulcanizates
| Sample of | Comparative formulation 1 | Comparative formulation 2 | Experimental formulation 1 | Experimental formulation 2 |
| Tensile strength, MPa | 24.7 | 25.0 | 26.0 | 26.6 |
| DIN abrasion volume, mm 3 /40m | 85 | 83 | 74 | 70 |
| Tanδ@60℃ | 0.162 | 0.160 | 0.148 | 0.140 |
| Compression heat, DEG C | 27.2 | 27.0 | 25.2 | 24.1 |
As can be seen from Table 2, the vulcanized rubber prepared with the powder rubber auxiliary agent has lower tensile strength, larger DIN abrasion volume (difference), higher Tan delta @60 ℃ shows higher rolling resistance (difference) and higher compression heat generation (difference). The tensile strength, DIN abrasion performance, rolling resistance and compression heat generation of comparative formulation 2 employing the conventional commercially available pre-dispersed rubber additive masterbatch are slightly improved. The pre-dispersed rubber auxiliary master batch prepared by the invention contains the reactive plasticizer low-Mooney trans-1, 4-diene copolymer, can promote the rubber auxiliary to be more uniformly dispersed under a formula system and participate in a crosslinking reaction during vulcanization, and meanwhile, the introduction of the low-Mooney trans-1, 4-diene copolymer can reduce the use of non-reactive plasticizer environment-friendly aromatic hydrocarbon oil under the formula system, so that the performance of preparing vulcanized rubber is obviously better.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. The vulcanized rubber is prepared from the following raw materials in parts by weight:
75-85 parts of natural rubber;
15-25 parts of butadiene rubber;
1-3 parts of stearic acid;
2-4 parts of an anti-aging agent;
45-55 parts of carbon black;
2-6 parts of aromatic oil;
0.2-32 parts of auxiliary agent master batch;
the auxiliary agent master batch is prepared from raw materials comprising a low-Mooney trans-1, 4-diene copolymer and a rubber auxiliary agent;
the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the rubber auxiliary agent is 20-50: 50-80 parts;
the Mooney viscosity of the low Mooney trans-1, 4-diene copolymer is 5-30; the low-Mooney trans-1, 4-diene copolymer is low-Mooney trans-butyl-pentyl rubber; in the low-Mooney trans-butyl-pentyl rubber, the molar content of butadiene structural units is less than or equal to 20% or more than or equal to 70%;
the rubber auxiliary agent comprises zinc oxide, an accelerator, a vulcanizing agent, a scorch retarder or an anti-reversion agent.
2. The curing adhesive of claim 1, wherein the accelerator comprises at least one of N-tert-butyl-2-benzothiazole sulfenamide, N-cyclohexyl-2-benzothiazole sulfenamide, dibenzothiazyl disulfide, and tetramethylthiuram disulfide;
the vulcanizing agent is selected from sulfur;
the scorch retarder is selected from N-cyclohexyl thio phthalimide;
the anti-reversion agent is selected from 1, 3-bis (citraconimidomethyl) benzene.
3. The vulcanized rubber according to claim 1, wherein the preparation method of the auxiliary master batch comprises the following steps:
and (3) carrying out banburying blending, extrusion granulation on the low-Mooney trans-1, 4-diene copolymer and the rubber auxiliary agent to obtain the pre-dispersed rubber auxiliary agent master batch.
4. The vulcanized rubber according to claim 3, wherein the banburying blending temperature is 55-65 ℃, the rotating speed is 45-55 rpm, and the time is 5-10 min;
the temperature of extrusion granulation is 65-75 ℃, and the rotating speed is 15-25 rpm.
5. The curing adhesive of claim 1, wherein the auxiliary master batch comprises a substance a, a substance b, a substance c and a substance d;
15-25 parts of a substance a;
the weight part of the substance b is 1-3 parts;
the weight part of the substance c is 1-3 parts;
the weight part of the substance d is 0.2-0.3 part;
the substance a is prepared from raw materials comprising low-Mooney trans-1, 4-diene copolymer and zinc oxide; in the substance a, the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the zinc oxide is 20-50: 50-80 parts;
the substance b is prepared from raw materials comprising a low-Mooney trans-1, 4-diene copolymer and an accelerator; in the substance b, the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the accelerator is 20-50: 50-80 parts;
the substance c is prepared from raw materials comprising a low-Mooney trans-1, 4-diene copolymer and a vulcanizing agent; in the substance c, the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the vulcanizing agent is 20-50: 50-80 parts;
the substance d is prepared from raw materials comprising a low-Mooney trans-1, 4-diene copolymer and a scorch retarder; in the substance d, the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the scorch retarder is 20-50: 50-80.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103756040A (en) * | 2014-01-08 | 2014-04-30 | 青岛科技大学 | Application of alkadiene polymer in rubber masterbatch, masterbatch and preparation method |
| WO2015109790A1 (en) * | 2014-01-23 | 2015-07-30 | 怡维怡橡胶研究院有限公司 | Composition from combination of trans-polyisoprene rubber and cis-polyisoprene rubber and process therefor |
| CN107814994A (en) * | 2017-11-20 | 2018-03-20 | 山东华聚高分子材料有限公司 | Reclaimed rubber that a kind of trans butadiene-isoprene rubber is modified and its production and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756040A (en) * | 2014-01-08 | 2014-04-30 | 青岛科技大学 | Application of alkadiene polymer in rubber masterbatch, masterbatch and preparation method |
| WO2015109790A1 (en) * | 2014-01-23 | 2015-07-30 | 怡维怡橡胶研究院有限公司 | Composition from combination of trans-polyisoprene rubber and cis-polyisoprene rubber and process therefor |
| CN107814994A (en) * | 2017-11-20 | 2018-03-20 | 山东华聚高分子材料有限公司 | Reclaimed rubber that a kind of trans butadiene-isoprene rubber is modified and its production and use |
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