CN114805959A - 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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- CN114805959A CN114805959A CN202210465531.2A CN202210465531A CN114805959A CN 114805959 A CN114805959 A CN 114805959A CN 202210465531 A CN202210465531 A CN 202210465531A CN 114805959 A CN114805959 A CN 114805959A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 108
- 239000005060 rubber Substances 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 27
- 229920001577 copolymer Polymers 0.000 claims abstract description 68
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 239000004596 additive masterbatch Substances 0.000 claims abstract description 28
- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 239000004636 vulcanized rubber Substances 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 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
- 238000002156 mixing Methods 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 229920002857 polybutadiene Polymers 0.000 claims description 22
- 239000005062 Polybutadiene Substances 0.000 claims description 21
- 229920003049 isoprene rubber Polymers 0.000 claims description 18
- 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
- 238000001125 extrusion Methods 0.000 claims description 13
- 238000005469 granulation Methods 0.000 claims description 13
- 230000003179 granulation Effects 0.000 claims description 13
- HNWAHFPYJHAAJE-UHFFFAOYSA-N n-tert-butyl-1,3-benzothiazole-2-sulfonamide Chemical compound C1=CC=C2SC(S(=O)(=O)NC(C)(C)C)=NC2=C1 HNWAHFPYJHAAJE-UHFFFAOYSA-N 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 229910045601 alloy Inorganic materials 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
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 229920005549 butyl rubber Polymers 0.000 claims description 5
- 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
- STSDHUBQQWBRBH-UHFFFAOYSA-N n-cyclohexyl-1,3-benzothiazole-2-sulfonamide Chemical compound N=1C2=CC=CC=C2SC=1S(=O)(=O)NC1CCCCC1 STSDHUBQQWBRBH-UHFFFAOYSA-N 0.000 claims description 2
- 239000010692 aromatic oil Substances 0.000 abstract description 9
- 238000004073 vulcanization Methods 0.000 abstract description 9
- 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
- 238000000034 method Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 238000009472 formulation Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 244000043261 Hevea brasiliensis Species 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 229920003052 natural elastomer Polymers 0.000 description 6
- 229920001194 natural rubber Polymers 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- 229920002943 EPDM rubber Polymers 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 238000003860 storage Methods 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
- 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 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 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
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- 229920003031 santoprene Polymers 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 241000795633 Olea <sea slug> Species 0.000 description 1
- -1 accelerators Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003292 glue Substances 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
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007858 starting material Substances 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention 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 additive masterbatch is prepared from raw materials comprising a low-Mooney trans-1, 4-diene copolymer and a rubber additive; the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the rubber additive is 20-50: 50-80 parts. The pre-dispersed rubber additive masterbatch contains the reactive plasticizer low-Mooney trans-1, 4-diene copolymer, so that the rubber additive 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, and the performance of preparing vulcanized rubber is obviously better. Vulcanized rubber prepared from the pre-dispersed rubber additive master batch has low rolling resistance and compression heat generation, and simultaneously has excellent 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 additives (such as accelerators, sulfur, zinc oxide and the like) are all filled in powder, and have more defects when providing special physical properties for rubber products, firstly, dust is generated in the using process, so that the metering is not accurate, 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-dispersing rubber additive masterbatch technology prepares common powdery rubber additives, carriers, modifiers and processing additives into granular rubber additives 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 very important, and the ethylene propylene diene monomer/ethylene-vinyl acetate copolymer rubber (EPDM/EVA), Butadiene Rubber (BR), nitrile rubber (NBR) and the like are adopted as more carriers in the current market in 'Chinese rubber' 2013. The EPDM/EVA system is used as a rubber auxiliary agent carrier, and has good quality stability in the storage process due to low unsaturated bond content, but is difficult to participate in crosslinking reaction under a sulfur vulcanization system; the content of saturated bonds such as BR and NBR is high, and the quality stability of the storage process is relatively poor.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a pre-dispersed rubber additive masterbatch, a preparation method and an application thereof, wherein vulcanized rubber prepared from the pre-dispersed rubber additive masterbatch has low rolling resistance and compression heat generation, and simultaneously has excellent wear resistance.
The invention provides a pre-dispersed rubber additive master batch which is prepared from raw materials comprising a low-Mooney trans-1, 4-diene copolymer and a rubber additive;
the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the rubber additive is 20-50: 50-80 parts.
Preferably, the Mooney viscosity of the low-Mooney trans-1, 4-diene copolymer is 5 to 30.
Preferably, the low-mooney trans-1, 4-diene copolymer comprises low-mooney trans-butyl-pentyl rubber or low-mooney trans-isoprene rubber in-kettle alloy.
Preferably, the low-Mooney trans-isoprene rubber kettle internal alloy is obtained by reacting low-Mooney trans-butadiene-isoprene rubber and low-Mooney trans-isoprene rubber;
in the raw materials for preparing the low-Mooney trans-isoprene rubber in the 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 rubber, the molar content of the butadiene structural unit is less than or equal to 20 percent or more than or equal to 70 percent.
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-tert-butyl-2-benzothiazole sulfonamide, N-cyclohexyl-2-benzothiazole sulfonamide, dibenzothiazyl disulfide and tetramethylthiuram disulfide;
the vulcanizing agent is selected from sulfur;
the scorch retarder is selected from N-cyclohexyl thiophthalimide;
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 banburying and blending the low-Mooney trans-1, 4-diene copolymer and the rubber additive, and extruding and granulating to obtain the pre-dispersed rubber additive master batch.
Preferably, the temperature of the banburying and blending 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 agent master batch comprises the pre-dispersed rubber auxiliary agent master batch or the pre-dispersed rubber auxiliary agent 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 the 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 a 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 the 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 parts.
The invention provides a pre-dispersed rubber additive master batch which is prepared from raw materials comprising a low-Mooney trans-1, 4-diene copolymer and a rubber additive; the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the rubber additive is 20-50: 50-80 parts. The pre-dispersed rubber additive masterbatch prepared by the invention contains the reactive plasticizer low-Mooney trans-1, 4-diene copolymer, so that the rubber additive 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, and the performance of preparing vulcanized rubber is obviously better. Vulcanized rubber prepared from the pre-dispersed rubber additive master batch has low rolling resistance and compression heat generation, and simultaneously has excellent wear resistance.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a pre-dispersed rubber additive master batch which is prepared from raw materials comprising a low-Mooney trans-1, 4-diene copolymer and a rubber additive;
the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the rubber additive is 20-50: 50-80 parts.
In certain embodiments of the present invention, the mass ratio of the low-mooney trans-1, 4-diene copolymer to the rubber coagent is 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 present invention, the low-mooney trans-1, 4-diene copolymer comprises a low-mooney trans-butadiene rubber or a low-mooney trans-isoprene rubber in-kettle 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-butadiene rubber has a molar content of butadiene structural units of 20% or more or 70% or more. In certain embodiments, the low-mooney trans-butadiene 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 santoprene co.
In certain embodiments of the present invention, the low-mooney trans-isoprene in-kettle alloy is obtained from the reaction of low-mooney trans-butadiene rubber and low-mooney trans-isoprene rubber. In certain embodiments of the invention, the low-mooney trans-isoprene in-kettle alloy is derived from santoprene co.
In some embodiments of the present invention, in the raw materials for preparing the low-mooney trans-isoprene rubber in-kettle alloy, the mass ratio of the low-mooney trans-butadiene rubber to the low-mooney trans-isoprene rubber is 15-25: 75-85.
In certain embodiments of the invention, the rubber coagent comprises zinc oxide, an accelerator, a vulcanizing agent, a scorch retarder, or an anti-reversion agent.
In certain embodiments of the present invention, the accelerator comprises at least one of N-tert-butyl-2-benzothiazolesulfenamide (NS), N-cyclohexyl-2-benzothiazolesulfenamide (CBS), dibenzothiazyl Disulfide (DM), and tetramethylthiuram disulfide (TMTD).
In certain embodiments of the present invention, the vulcanizing agent is selected from sulfur.
In certain embodiments of the present invention, the scorch retarder is selected from N-Cyclohexyl Thiophthalimide (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 banburying and blending the low-Mooney trans-1, 4-diene copolymer and the rubber additive, and extruding and granulating to obtain the pre-dispersed rubber additive master batch.
In some embodiments of the invention, the banburying and blending are carried out at the temperature of 55-65 ℃, the rotation speed of 45-55 rpm and the time of 5-10 min. In certain embodiments of the present invention, the banburying blending is performed at 60 ℃ and 50rpm for 5 min.
In some embodiments of the present invention, the temperature of the extrusion granulation is 65 to 75 ℃, and the rotation speed is 15 to 25 rpm. In certain embodiments of the invention, the extrusion granulation is at a temperature of 70 ℃ and a speed of 20 rpm.
In the invention, the preparation of the pre-dispersed rubber auxiliary master batch needs two processes of banburying and blending and extrusion granulation; the method can adopt an internal mixer to carry out internal mixing and blending, and a screw extruder to carry out extrusion granulation, and can also adopt one screw extruder to simultaneously realize the internal mixing and extrusion granulation of the low-Mooney trans-1, 4-dialkene copolymer and the rubber auxiliary agent.
The invention also provides vulcanized rubber which is prepared from the following raw materials in parts by weight:
the additive masterbatch comprises the pre-dispersed rubber additive masterbatch described above or comprises the pre-dispersed rubber additive masterbatch prepared by the preparation method described above.
In some embodiments of the present invention, the auxiliary masterbatch 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 a 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 the 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 parts.
In the vulcanized rubber, the components and the properties of the low-Mooney trans-1, 4-diene copolymer are the same as above and are not described in detail herein.
In certain embodiments of the present invention, the natural rubber is present in an amount of 80 parts by weight. In certain embodiments of the invention, the natural rubber is available under the designation SCRWF and is produced by the marine rubber group.
In certain embodiments of the present invention, the weight fraction of the butadiene rubber is 20 parts. In certain embodiments of the invention, the cis-butadiene rubber is available under the designation BR 9000, manufactured by the olea petrochemical rubber division.
In certain embodiments of the present invention, the weight part 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 present invention, the mass ratio of the low-mooney trans-1, 4-diene copolymer and zinc oxide in the substance a is 40: 60 or 20: 80.
in the present 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 banburying, blending, extruding and granulating the low-Mooney trans-1, 4-diene copolymer and zinc oxide to obtain a substance a.
In certain embodiments of the present invention, the temperature of the banburying blending is 60 ℃, the rotation speed is 50rpm, and the time is 5 min;
in certain embodiments of the invention, the extrusion granulation is at a temperature of 70 ℃ and a speed of 20 rpm.
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 invention, the antioxidant is present in an amount of 3 parts by weight. In certain embodiments of the invention, the antioxidant comprises N- (1, 3-dimethyl) butyl-N' -phenyl-p-phenylenediamine (antioxidant 4020) and a polymer of 2,2, 4-trimethyl-1, 2-dihydroquinoline (antioxidant RD), the mass ratio of antioxidant 4020 to antioxidant RD being 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 present invention, the weight fraction of the aromatic oil is 6 parts or 2 parts. In certain embodiments of the invention, the aromatic oil is selected from VIVATEC 500, manufactured by hanseng petrochemical (ningbo) ltd.
In certain embodiments of the present invention, the weight part 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 accelerant is NS.
In certain embodiments of the invention, the mass ratio of the low-mooney trans-1, 4-diene copolymer and the 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 predispersed rubber auxiliary master batch described above. In certain embodiments of the invention, substance b is prepared according to the following method:
and banburying and blending the low-Mooney trans-1, 4-diene copolymer and the accelerator, and extruding and granulating to obtain a substance b.
In certain embodiments of the present invention, the temperature of the banburying blending is 60 ℃, the rotation speed is 50rpm, and the time is 5 min;
in certain embodiments of the invention, the extrusion granulation is at a temperature of 70 ℃ and a speed of 20 rpm.
In certain embodiments of the present invention, the weight part of the substance c is 2 parts.
In the present invention, the substance c is prepared from raw materials comprising a low-Mooney trans-1, 4-diene copolymer and a vulcanizing agent.
In certain embodiments of the present invention, the mass ratio of the low-mooney trans-1, 4-diene copolymer and the vulcanizing agent in the 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 predispersed rubber auxiliary masterbatch described above. In certain embodiments of the invention, substance c is prepared according to the following method:
and banburying and blending the low-Mooney trans-1, 4-diene copolymer and a vulcanizing agent, and extruding and granulating to obtain a substance c.
In certain embodiments of the present invention, the temperature of the banburying blending is 60 ℃, the rotation speed is 50rpm, and the time is 5 min;
in certain embodiments of the invention, the extrusion granulation is at a temperature of 70 ℃ and a speed of 20 rpm.
In certain embodiments of the present invention, the weight part of the substance d is 0.25 parts.
In the present invention, the substance d is prepared from raw materials 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 present invention, the mass ratio of the low-mooney trans-1, 4-diene copolymer and the scorch retarder in substance d is 20: 80.
in the present invention, the preparation method of the substance d is the same as the preparation method of the predispersed rubber auxiliary masterbatch described above. In certain embodiments of the invention, substance d is prepared according to the following method:
and banburying, blending, extruding and granulating the low-Mooney trans-1, 4-diene copolymer and the scorch retarder to obtain a substance d.
In certain embodiments of the present invention, the temperature of the banburying blending is 60 ℃, the rotation speed is 50rpm, and the time is 5 min;
in certain embodiments of the invention, the extrusion granulation is at a temperature of 70 ℃ and a speed of 20 rpm.
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 rubber;
B) mixing the first-stage rubber, the substance b, the substance c and the substance d, and banburying to obtain second-stage rubber;
C) and vulcanizing the two-stage dense rubber to obtain vulcanized rubber.
In the preparation method of the vulcanized rubber, the adopted raw material components
In step A):
in certain embodiments of the present invention, the temperature of the banburying is 65 to 75 ℃. In certain embodiments, the temperature of the banburying is 70 ℃.
In some embodiments of the invention, the banburying has a rotation speed of 60-80 r/min. In some embodiments, the banburying speed is 70 r/min.
In certain embodiments of the present invention, the banburying time is 1 min.
In some embodiments of the invention, the temperature for continuous banburying is 65-75 ℃. In certain embodiments, the temperature for the continued banburying is 70 ℃.
In some embodiments of the invention, the rotation speed of the continuous banburying is 60-80 r/min. In some embodiments, the rotation speed for continuous banburying is 70 r/min.
In some embodiments of the invention, the continuous banburying time is 3-5 min. In some embodiments, the mixing is continued for 3 min.
In some embodiments of the present invention, after the banburying is completed, the method further includes: cleaning the upper top bolt of the internal mixer, and discharging the rubber and then discharging the rubber.
In some embodiments of the present invention, after obtaining a batch, the method further comprises: standing at room temperature. In certain embodiments, the room temperature rest time is 2 hours.
In step B):
in certain embodiments of the present invention, the temperature of the banburying is 45-55 ℃. In certain embodiments, the temperature of said banburying is 50 ℃.
In some embodiments of the invention, the banburying has a rotation speed of 40-60 r/min. In some embodiments, the banburying is performed at a speed of 50 r/min.
In some embodiments of the present invention, the banburying time is 1-2 min. In certain embodiments, the banburying time is 1.5 min.
In some embodiments of the present invention, after the banburying, the method further comprises: and (5) removing the glue and then discharging the sheet.
In some embodiments of the present invention, after obtaining the secondary rubber batch, the method further comprises: standing at room temperature. In certain embodiments, the room temperature rest time is 1 d.
In step C):
in some 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 present invention, the pressure of the vulcanization is 8 to 12 MPa. In certain embodiments, the pressure of the sulfiding is 10 MPa.
In some embodiments of the present invention, the time for the vulcanization is 10 to 20 min. In certain embodiments, the time for vulcanization is 15 min.
The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.
In the invention, when the low-Mooney trans-1, 4-diene copolymer is mixed with the powder rubber additive, processing aids 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 additive master batch is not adhered in the storage process on the premise of not using an anti-adhesion agent; the pre-dispersed rubber additive masterbatch prepared by adopting the low-Mooney trans-1, 4-diene copolymer has good fluidity and good dispersion effect when used in a rubber formula; the low-Mooney trans-1, 4-diene copolymer can participate in a vulcanization crosslinking reaction when used in a rubber product, and the prepared vulcanized rubber has more excellent application performance.
In order to further illustrate the present invention, the following examples are provided to describe the pre-dispersed rubber auxiliary masterbatch, the preparation method and the application thereof in detail, but they should not be construed as limiting the scope of the present invention.
The starting materials used in the following examples are all generally commercially available.
In the examples, the natural rubber is designated as SCRWF and produced by sea rubber group; the grade of the butadiene rubber is BR 9000, and is produced by Qilu petrochemical rubber division; the aromatic oil is selected from VIVATEC 500 produced by Hansen petrochemical (Ningbo) Co.
Example 1
Preparing pre-dispersed rubber auxiliary master batch:
mixing low-Mooney trans-butadiene rubber (the molar content of a butadiene structural unit is 20 percent, the Mooney viscosity is 30) and an accelerator N-tert-butyl-2-benzothiazole sulfonamide (NS) according to a mass ratio of 50: 50, putting into an internal mixer, and carrying out internal mixing for 5min, wherein the rotating speed of the internal mixer is as follows: 50rpm, initial temperature 60 ℃ and then, in a twin-screw extruder, extrusion granulation was carried out at a screw temperature of 70 ℃ and a rotation speed of 20rpm, to obtain substance b1(NS-50 sample).
Replacing the mass ratio of the low-Mooney trans-butyl-pentyl rubber to an accelerator N-tert-butyl-2-benzothiazole sulfonamide (NS) with 20: 80, and the remaining steps were carried out as described above, to give substance b2(NS-80 sample).
Example 2
Preparing a pre-dispersed rubber additive master batch:
mixing low-Mooney trans-butadiene rubber (the molar content of a butadiene structural unit is 5 percent, the Mooney viscosity is 5) and zinc oxide (ZnO) according to a mass ratio of 40: 60, feeding into an internal mixer, mixing for 5min, wherein the rotating speed of the internal mixer is as follows: 50rpm, initial temperature 60 ℃, and then, extruding and granulating in a double screw extruder at a screw temperature of 70 ℃ and a rotation speed of 20rpm to obtain a substance a1(ZnO-60 sample).
Replacing the mass ratio of the low-mooney trans-butyl rubber to zinc oxide by 20: 80, and the rest of the steps are carried out according to the steps to prepare a substance a2(ZnO-80 sample).
Example 3
Preparing a pre-dispersed rubber additive master batch:
mixing low-Mooney trans-butadiene rubber (the molar content of a butadiene structural unit is 75%, the Mooney viscosity is 15) and sulfur powder (S) according to the mass ratio of 50: 50, putting into an internal mixer, and carrying out internal mixing for 5min, wherein the rotating speed of the internal mixer is as follows: 50rpm, initial temperature 60 ℃ and then, extrusion granulation was carried out in a twin-screw extruder at a screw temperature of 70 ℃ and a rotation speed of 20rpm, to obtain substance c1 (sample S-50).
Replacing the mass ratio of the low-Mooney trans-butyl-pentyl rubber to the sulfur powder by 20: 80, and the remaining steps were carried out as described above to give substance c2 (sample S-80).
Example 4
Preparing pre-dispersed rubber auxiliary master batch:
mixing low-Mooney trans-butadiene rubber (the molar content of butadiene structural units is 95 percent, the Mooney viscosity is 10) and a scorch retarder (CTP) according to the mass ratio of 20: 80, putting into an internal mixer, and carrying out internal mixing for 5min, wherein the rotating speed of the internal mixer is as follows: 50rpm, initial temperature 60 ℃, and then, extruding and granulating in a double screw extruder at a screw temperature of 70 ℃ and a rotation speed of 20rpm to obtain a substance d (CTP-80 sample).
Example 5
A rubber 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, antioxidant, carbon black and aromatic oil, continuing banburying for 3min, cleaning an upper top bolt of the banbury mixer, discharging rubber for 5min, and then discharging rubber from a mill to obtain a section of banburying rubber; standing at room temperature for 2 h;
2) mixing the first-stage rubber 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 rubber compound; standing at room temperature for 1 d;
C) and vulcanizing the two-stage dense rubber for 15min at 150 ℃ and 10MPa to obtain vulcanized rubber.
Wherein, the zinc oxide, the accelerator NS, the sulfur and the antiscorching agent CTP used in the comparative formula 1 are all in a powder state, the commercially available pre-dispersed rubber additive masterbatch is used in the comparative formula 2, and the novel pre-dispersed rubber additive masterbatch prepared in the embodiment of the present invention is used in the experimental formula.
Table 1 comparative and experimental formulations
| Sample (I) | Comparative formulation 1 | Comparative formulation 2 | Experimental formulation 1 | Experimental formulation 2 |
| Natural rubber | 80 | 80 | 80 | 80 |
| Cis-polybutadiene rubber | 20 | 20 | 20 | 20 |
| Zinc oxide (powder) | 6.0 | 0 | 0 | 0 |
| ZnO-80 (commercially available) | 0 | 7.5 | 0 | 0 |
| ZnO-60 (preparation of example 2, a1) | 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 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 |
| Accelerator NS-80 (preparation of example 1, b2) | 0 | 0 | 2.0 | 2.0 |
| Sulfur (powder) | 1.6 | 0 | 0 | 0 |
| S-80 (commercially available) | 0 | 2.0 | 0 | 0 |
| S-80 (preparation of example 3, c2) | 0 | 0 | 2.0 | 2.0 |
| Scorch retarder CTP (powder) | 0.2 | 0 | 0 | 0 |
| CTP-80 (commercially available) | 0 | 0.25 | 0 | 0 |
| CTP-80 (preparation of example 4, d) | 0 | 0 | 0.25 | 0.25 |
The properties of the vulcanizates obtained were tested. The tensile strength of the vulcanizate was tested using a Zwick/Roell 2005 electronic tensile tester, manufactured by Zwick/Roell, Germany, in accordance with the standard GB/T528-2009. The MZ-4060 drum-type abrasion machine produced by Jiangsu Mingzhu testing machinery Limited company is adopted to test DIN abrasion performance according to the standard GB/T9867, and the load weight is as follows: 10 + -0.2N. The compression heat generation of the test sample is tested by adopting a GT-RH-2000 type compression heat generation testing machine produced by Taiwan high-speed railway science and technology Co., Ltd, and the test conditions are as follows: the temperature is 55 plus or minus 1 ℃, the stroke is 4.45 plus or minus 0.03mm, and the load is 1.00 plus or minus 0.03 MPa. 861 manufactured by Switzerland Mettler corporation is adopted e The dynamic thermomechanical property analyzer tests the tan delta value, the frequency of 10Hz and the strain of 5.0 percent of vulcanized rubber at 60 ℃. The results are shown in Table 2.
TABLE 2 Property test results of vulcanizates
| Sample (I) | 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 |
| Heat generation by compression, DEG C | 27.2 | 27.0 | 25.2 | 24.1 |
As can be seen from Table 2, the vulcanizates prepared with the powder rubber coagent had lower tensile strength, greater (poor) DIN abrasion volume, and higher Tan delta @60 ℃ indicating higher (poor) rolling resistance and higher (poor) heat build-up from compression. Comparative formulation 2, which employed the conventional commercially available predispersed rubber aid masterbatch, had slightly improved tensile strength, DIN abrasion performance, rolling resistance and heat generation from compression. The pre-dispersed rubber additive masterbatch prepared by the invention contains the reactive plasticizer low-Mooney trans-1, 4-diene copolymer, so that the rubber additive 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, and 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 (10)
1. A pre-dispersed rubber additive master batch is prepared from raw materials comprising a low-Mooney trans-1, 4-diene copolymer and a rubber additive;
the mass ratio of the low-Mooney trans-1, 4-diene copolymer to the rubber additive is 20-50: 50-80 parts.
2. The predispersed rubber auxiliary masterbatch according to claim 1, wherein the low-Mooney trans-1, 4-diene copolymer has a Mooney viscosity of 5 to 30.
3. The predispersed rubber aid masterbatch according to claim 1, wherein the low-mooney trans-1, 4-diene copolymer comprises a low-mooney trans-butyl rubber or a low-mooney trans-isoprene rubber in-kettle alloy.
4. The predispersed rubber additive masterbatch according to claim 3, wherein the low-Mooney trans-isoprene rubber in-kettle alloy is obtained by reacting low-Mooney trans-butadiene-isoprene rubber with low-Mooney trans-isoprene rubber;
in the raw materials for preparing the low-Mooney trans-isoprene rubber in the kettle, the mass ratio of the low-Mooney trans-butadiene-isoprene rubber to the low-Mooney trans-isoprene rubber is (15-25): 75-85.
5. The predispersed rubber auxiliary masterbatch according to any one of claims 3 or 4, wherein the low-Mooney trans-butadiene rubber has a molar content of butadiene structural units of 20% or more or 70% or more.
6. The predispersed rubber additive masterbatch of claim 1 wherein the rubber additive comprises zinc oxide, an accelerator, a vulcanizing agent, a scorch retarder, or an anti-reversion agent;
the accelerator comprises at least one of N-tert-butyl-2-benzothiazole sulfonamide, N-cyclohexyl-2-benzothiazole sulfonamide, dibenzothiazyl disulfide and tetramethylthiuram disulfide;
the vulcanizing agent is selected from sulfur;
the scorch retarder is selected from N-cyclohexyl thiophthalimide;
the anti-reversion agent is selected from 1, 3-bis (citraconimidomethyl) benzene.
7. A preparation method of a pre-dispersed rubber auxiliary master batch comprises the following steps:
and banburying and blending the low-Mooney trans-1, 4-diene copolymer and the rubber additive, and extruding and granulating to obtain the pre-dispersed rubber additive master batch.
8. The preparation method of claim 7, wherein the banburying and blending temperature is 55-65 ℃, the rotation 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.
9. The vulcanized rubber is prepared from the following raw materials in parts by weight:
the auxiliary agent master batch comprises the pre-dispersed rubber auxiliary agent master batch of any one of claims 1 to 6, or the pre-dispersed rubber auxiliary agent master batch prepared by the preparation method of any one of claims 7 to 8.
10. The vulcanizate of claim 9, wherein the additive masterbatch comprises a substance a, a substance b, a substance c, and a substance d;
15-25 parts of the 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 a 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 the 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 parts.
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Citations (3)
| 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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