CN115160657A - Rubber masterbatch and preparation method thereof - Google Patents
Rubber masterbatch and preparation method thereof Download PDFInfo
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- CN115160657A CN115160657A CN202210987458.5A CN202210987458A CN115160657A CN 115160657 A CN115160657 A CN 115160657A CN 202210987458 A CN202210987458 A CN 202210987458A CN 115160657 A CN115160657 A CN 115160657A
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- rubber
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- auxiliary agent
- master batch
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 270
- 239000005060 rubber Substances 0.000 title claims abstract description 270
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 90
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 45
- 239000011159 matrix material Substances 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 23
- 239000000725 suspension Substances 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011593 sulfur Substances 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 238000012662 bulk polymerization Methods 0.000 claims description 48
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 42
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 33
- 229920003051 synthetic elastomer Polymers 0.000 claims description 33
- 239000005061 synthetic rubber Substances 0.000 claims description 33
- 244000043261 Hevea brasiliensis Species 0.000 claims description 32
- 229920003052 natural elastomer Polymers 0.000 claims description 32
- 229920001194 natural rubber Polymers 0.000 claims description 32
- 239000003292 glue Substances 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 239000006229 carbon black Substances 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 239000004568 cement Substances 0.000 claims description 14
- 239000004014 plasticizer Substances 0.000 claims description 14
- 229920003049 isoprene rubber Polymers 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 claims description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- 239000012744 reinforcing agent Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 239000008096 xylene Substances 0.000 claims description 9
- 239000010692 aromatic oil Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 5
- 239000002612 dispersion medium Substances 0.000 claims description 5
- 239000004200 microcrystalline wax Substances 0.000 claims description 5
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 3
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 claims description 3
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 3
- 239000005662 Paraffin oil Substances 0.000 claims description 2
- -1 in the i Substances 0.000 claims 1
- ZJNLYGOUHDJHMG-UHFFFAOYSA-N 1-n,4-n-bis(5-methylhexan-2-yl)benzene-1,4-diamine Chemical compound CC(C)CCC(C)NC1=CC=C(NC(C)CCC(C)C)C=C1 ZJNLYGOUHDJHMG-UHFFFAOYSA-N 0.000 claims 1
- 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 claims 1
- 230000020169 heat generation Effects 0.000 abstract description 18
- 238000005096 rolling process Methods 0.000 abstract description 17
- 239000000945 filler Substances 0.000 abstract description 11
- 238000004073 vulcanization Methods 0.000 abstract description 10
- 229920006247 high-performance elastomer Polymers 0.000 abstract description 7
- 239000004636 vulcanized rubber Substances 0.000 abstract description 6
- 238000013016 damping Methods 0.000 abstract description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 20
- 230000003712 anti-aging effect Effects 0.000 description 19
- 230000006835 compression Effects 0.000 description 13
- 238000007906 compression Methods 0.000 description 13
- 239000011787 zinc oxide Substances 0.000 description 11
- 235000021355 Stearic acid Nutrition 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 7
- 239000008117 stearic acid Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 239000002671 adjuvant Substances 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
- C08J3/212—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase and solid additives
-
- 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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J2309/00—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
- 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
- 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
- C08J2409/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The invention provides a rubber master batch and a preparation method thereof. The preparation method provided by the invention comprises the steps of a) providing a rubber solution, specifically providing the rubber solution in three forms i to iii; mixing the rubber solution with an auxiliary agent or an auxiliary agent suspension to obtain a mixed solution; then, removing the solvent from the mixed solution to obtain a master batch matrix; finally, mixing and banburying the rubber, an accelerator, sulfur and an auxiliary agent to obtain rubber master batch; wherein the rubber comprises the masterbatch matrix; the mass percentage of the master batch matrix in the rubber is 14-100%. The high-performance rubber masterbatch is prepared by adopting a wet method, compared with the dry method masterbatch, the filler dispersibility is greatly improved, and better associativity is formed between the high-performance rubber masterbatch and other components, so that vulcanized rubber obtained after vulcanization has excellent mechanical property and wear resistance, and rolling resistance and heat generation are effectively reduced; can be applied to the fields of tires, damping elastic elements, rubber belts and the like.
Description
Technical Field
The invention relates to the field of rubber processing, and particularly relates to a rubber master batch and a preparation method thereof.
Background
With the development of the rubber industry, the requirements of products such as tires, damping elastic elements, rubber belts and the like on performance are higher and higher, the general method adopts rubber, reinforcing agent and other additives to be mixed and then vulcanized in a dry mechanical blending mode, and the preparation process of the method has the following defects although the operation is simple: the reinforcing agent and other powder additives are easy to fly, so that the composition of a finished product is inconsistent with the original design composition, the environment is polluted, the energy consumption is high and the like, and meanwhile, the dispersing effect of the reinforcing agent and other additives in a rubber matrix is poor, so that the application performance of a rubber product is seriously influenced.
The development of the wet mixing process technology provides a new preparation way for high-performance rubber products. The patent CN102414270A mentions the application of a master batch matrix rubber composition in a tire, and describes a process for preparing a master batch matrix by mixing two of a dispersion liquid of a white turbidity-like rubber auxiliary (an antioxidant, stearic acid, resin, etc.), a rubber latex and a filler slurry, and then mixing the two with another liquid. The American cabot company develops a preparation process for continuously preparing natural rubber/carbon black master batch by liquid phase (US 6048923A, CN97195156. X) by using natural latex and carbon black water slurry, simplifies the rubber mixing process, shortens the mixing time, and reduces the energy consumption and the cost, but the variety of the master batch and the variety of the filler are limited, and simultaneously, the polar components of the latex are adsorbed on the surface of the filler to destroy the interaction between the filler and the rubber, so that the application performance of the obtained rubber product is greatly reduced.
Disclosure of Invention
In view of the above, the present invention aims to provide a rubber masterbatch, a preparation method thereof, and a rubber composite material. The rubber master batch provided by the invention can effectively reduce the rolling resistance and heat generation of materials and improve the wear resistance.
The invention provides a preparation method of rubber master batch, which comprises the following steps:
a) Providing a rubber solution, specifically as follows:
dissolving rubber in a solvent to obtain a rubber dissolving solution;
or
ii, providing a bulk polymerization rubber glue solution;
or
iii, mixing the rubber dissolving solution with the bulk polymerization rubber glue solution to obtain a rubber mixed solution;
b) Mixing the rubber solution provided in the step a) with an auxiliary agent or an auxiliary agent suspension to obtain a mixed solution;
c) Removing the solvent from the mixed solution to obtain a master batch matrix;
d) Mixing and banburying rubber, an accelerator, sulfur and an auxiliary agent to obtain rubber master batch;
the rubber comprises the masterbatch matrix; the mass percentage of the master batch matrix in the rubber is 14-100%;
wherein the content of the first and second substances,
in the i, the rubber is synthetic rubber or synthetic rubber and natural rubber; wherein the synthetic rubber is formed by taking at least one of a butadiene monomer, an isoprene monomer and a styrene monomer as a raw material;
in the ii, the rubber in the bulk polymerization rubber glue solution is formed by taking at least one of a butadiene monomer, an isoprene monomer and a styrene monomer as a raw material;
in the step iii, the rubber in the bulk polymerization rubber glue solution is formed by taking at least one of a butadiene monomer, an isoprene monomer and a styrene monomer as a raw material; the rubber in the rubber dissolving liquid is synthetic rubber or synthetic rubber and natural rubber, and is different from the rubber in the bulk polymerization rubber liquid.
Preferably, in the i, the rubber is trans-1, 4-butadiene-isoprene copolymer rubber or trans-1, 4-butadiene-isoprene copolymer rubber and natural rubber;
in the ii, the bulk polymerization rubber cement is a bulk polymerization trans-1, 4-butadiene-isoprene rubber cement;
in the step iii, the bulk polymerization rubber glue solution is a bulk polymerization trans-1, 4-butadiene-isoprene rubber glue solution; the rubber in the rubber solution is other rubber except the trans-1, 4-butadiene-isoprene copolymer rubber, and the other rubber is natural rubber or cis-1, 4-polyisoprene rubber.
Preferably, the mass percentage concentration of the rubber solution provided in the step a) is 5-40%.
Preferably, the auxiliary agent in the step b) comprises the following components based on 100 parts by mass of the rubber in the rubber solution provided in the step a):
wherein, the first and the second end of the pipe are connected with each other,
the reinforcing agent is one or more of carbon black, white carbon black, argil, calcium carbonate, graphene and carbon nano tubes;
the coupling agent is a silane coupling agent;
the auxiliary agent in the step d) comprises the following components in parts by mass based on 100 parts by mass of the rubber in the rubber solution provided in the step a):
besides the plasticizer and the scorch retarder, the dosage of the auxiliary agent in the step d) and the same type of components in the auxiliary agent in the step b) is not 0 simultaneously.
Preferably, the silane coupling agent is one or more of silane coupling agents Si-69, si-75, KH550, KH560 and KH 570.
Preferably, the anti-aging agent is selected from one or more of anti-aging agent 4020, anti-aging agent RD, anti-aging agent 4010NA, anti-aging agent AW, anti-aging agent 4030 and microcrystalline wax;
the plasticizer is selected from one or more of aromatic oil, paraffin oil and naphthenic oil;
the scorch retarder is a scorch retarder CTP.
Preferably, in the step i, the mass ratio of the synthetic rubber in the mixed rubber of the synthetic rubber and the natural rubber is 5 to 50%.
Preferably, in the step i, the solvent is selected from one or more of n-heptane, n-hexane, cyclohexane, toluene, xylene and tetrahydrofuran;
in the iii, the solvent in the rubber dissolving solution is selected from one or more of n-heptane, n-hexane, cyclohexane, toluene, xylene and tetrahydrofuran;
in the step b), the dispersion medium in the auxiliary agent suspension is selected from one or more of n-heptane, n-hexane, cyclohexane, toluene, xylene and tetrahydrofuran;
in the auxiliary agent suspension, the dosage ratio of the auxiliary agent to the dispersing medium is (10-100) g to (50-1000) mL.
Preferably, in step D), the accelerator is selected from one or more of accelerator NS, accelerator CBS, accelerator DPG, accelerator NOBS, accelerator TMTD and accelerator D;
based on 100 parts by mass of the rubber in the rubber solution provided in the step a), the amount of the accelerator is 1.0-2.5 parts, and the amount of the sulfur is 1.0-2.5 parts.
The invention also provides the rubber master batch prepared by the preparation method in the technical scheme.
The preparation method provided by the invention comprises the steps of a) providing a rubber solution, specifically providing the rubber solution in three forms i to iii; mixing the rubber solution with an auxiliary agent or an auxiliary agent suspension to obtain a mixed solution; then, removing the solvent from the mixed solution to obtain a master batch matrix; finally, mixing and banburying rubber, an accelerator, sulfur and an auxiliary agent to obtain rubber master batch; wherein the rubber comprises the masterbatch matrix; the mass percentage of the master batch matrix in the rubber is 14-100%. The high-performance rubber masterbatch is prepared by adopting a wet method, compared with the dry method masterbatch, the filler dispersibility is greatly improved, and better associativity is formed between the high-performance rubber masterbatch and other components, so that vulcanized rubber obtained after vulcanization has excellent mechanical property and wear resistance, and rolling resistance and heat generation are effectively reduced; can be applied to the fields of tires, damping elastic elements, rubber belts and the like.
The experimental result shows that the tensile strength of the rubber product obtained by the invention is more than 26MPa, the tear strength is more than 96KN/m, the rebound resilience is more than 52 percent, the compression heat generation is below 40 ℃, the rolling resistance tan delta @60 ℃ is below 0.215, and the DIN abrasion is 99mm 3 Less than 40m, excellent mechanical property and wear resistance, and lower compression heat generation and rolling resistance.
Detailed Description
The invention provides a preparation method of rubber master batch, which comprises the following steps:
a) Providing a rubber solution, specifically as follows:
dissolving rubber in a solvent to obtain a rubber dissolving solution;
or
ii, providing a bulk polymerization rubber glue solution;
or
Mixing the rubber dissolving solution with the bulk polymerization rubber glue solution to obtain a rubber mixed solution;
b) Mixing the rubber solution provided in the step a) with an auxiliary agent or an auxiliary agent suspension to obtain a mixed solution;
c) Removing the solvent from the mixed solution to obtain a master batch matrix;
d) Mixing and banburying rubber, an accelerator, sulfur and an auxiliary agent to obtain rubber master batch;
the rubber comprises the masterbatch matrix; the mass percentage of the master batch matrix in the rubber is 14-100%;
wherein the content of the first and second substances,
in the i, the rubber is synthetic rubber or synthetic rubber and natural rubber; wherein the synthetic rubber is formed by taking at least one of a butadiene monomer, an isoprene monomer and a styrene monomer as a raw material;
in the ii, the rubber in the bulk polymerization rubber glue solution is formed by taking at least one of a butadiene monomer, an isoprene monomer and a styrene monomer as a raw material;
in the step iii, the rubber in the bulk polymerization rubber glue solution is formed by taking at least one of a butadiene monomer, an isoprene monomer and a styrene monomer as a raw material; the rubber in the rubber dissolving liquid is synthetic rubber or synthetic rubber and natural rubber, and is different from the rubber in the bulk polymerization rubber liquid.
According to the preparation method provided by the invention, the high-performance rubber master batch is prepared by adopting a wet method, compared with a dry method master batch, the filler dispersibility is greatly improved, and better associativity is formed between the filler and other components, so that vulcanized rubber obtained after vulcanization has excellent mechanical property and wear resistance, and rolling resistance and heat generation are effectively reduced; can be applied to the fields of tires, damping elastic elements, rubber belts and the like.
[ with respect to step a ]:
a) A rubber solution is provided.
In the invention, the rubber in the rubber solution provided by the step a) contains synthetic rubber, and the synthetic rubber is formed by taking at least one of butadiene monomer, isoprene monomer and styrene monomer as raw materials.
In the invention, the rubber solution provided in step a) is specifically as follows:
dissolving rubber in a solvent to obtain a rubber dissolving solution;
or
ii, providing a bulk polymerization rubber glue solution;
or
And iii, mixing the rubber dissolving solution with the bulk polymerization rubber glue solution to obtain a rubber mixed solution.
Regarding i:
the rubber is synthetic rubber or mixed rubber of the synthetic rubber and natural rubber. Wherein the synthetic rubber is formed by taking at least one of butadiene monomer, isoprene monomer and styrene monomer as raw materials, and is preferably trans-1, 4-butadiene-isoprene copolymer rubber; in some embodiments of the invention, trans-1, 4-butadiene-isoprene copolymer rubber TBIR 2249 is employed. The type of the natural rubber is not particularly limited, and may be a natural rubber conventionally used in the art, and in some embodiments of the present invention, the natural rubber is SCRWF. When the rubber is a mixed rubber of synthetic rubber and natural rubber, the mass ratio of the synthetic rubber to the total rubber is preferably 5% to 50%, and specifically may be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%.
The solvent is preferably one or more of n-heptane, n-hexane, cyclohexane, toluene, xylene and tetrahydrofuran.
The mass percentage concentration of the rubber solution obtained by dissolving rubber in the solvent is preferably 5% to 40%, and specifically may be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%.
With respect to ii:
the rubber in the bulk polymerization rubber cement is formed by taking at least one of butadiene monomer, isoprene monomer and styrene monomer as a raw material, and is more preferably trans-1, 4-butadiene-isoprene copolymer rubber, namely the cement is bulk polymerization trans-1, 4-butadiene-isoprene copolymer rubber cement. The bulk polymerization rubber cement is rubber cement prepared by using a bulk polymerization process, the bulk polymerization process is not particularly limited by the invention, and the bulk polymerization process is only a conventional bulk polymerization process in the field, such as a bulk polymerization process disclosed in the prior art CN 201610173038.8.
The mass percentage concentration of the mass polymerization rubber glue solution is preferably 5-40%, and specifically can be 5%, 10%, 15%, 20%, 25%, 30%, 35% and 40%.
With respect to iii:
the rubber in the bulk polymerization rubber glue solution is formed by taking at least one of a butadiene monomer, an isoprene monomer and a styrene monomer as a raw material, and is more preferably trans-1, 4-butadiene-isoprene copolymer rubber, namely the glue solution is a bulk polymerization trans-1, 4-butadiene-isoprene copolymer rubber glue solution. The bulk polymerization rubber cement is rubber cement prepared by using a bulk polymerization process, and the bulk polymerization process is not particularly limited and only needs to be a conventional bulk polymerization process in the field. The mass percentage concentration of the bulk polymerization rubber glue solution is preferably 5-40%, and specifically can be 5%, 10%, 15%, 20%, 25%, 30%, 35% and 40%.
The rubber in the rubber dissolving solution is synthetic rubber, or synthetic rubber and natural rubber, and is different from the rubber in the bulk polymerization rubber glue solution in the step iii. The rubber in the rubber-dissolved liquid is more preferably a rubber other than the trans-1, 4-butadiene-isoprene copolymer rubber, and the rubber is natural rubber or cis-1, 4-polyisoprene rubber.
Wherein the synthetic rubber is formed by taking at least one of butadiene monomer, isoprene monomer and styrene monomer as raw material, and is more preferably cis-1, 4-polyisoprene rubber; in some embodiments of the invention, cis-1, 4-polyisoprene rubber SKI-3 is employed.
When the rubber in the rubber solution is a mixed rubber of synthetic rubber and natural rubber, the mass ratio of the synthetic rubber to the total rubber is preferably 5% to 50%, and specifically may be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%. The type of the natural rubber is not particularly limited, and may be any natural rubber that is conventional in the art, and in some embodiments of the present invention, the natural rubber is SCR WF. Among them, the synthetic rubber is preferably a synthetic rubber other than the trans-1, 4-butadiene-isoprene copolymer rubber, and more preferably a cis-1, 4-polyisoprene rubber.
The solvent in the rubber dissolving liquid is preferably one or more of n-heptane, n-hexane, cyclohexane, toluene, xylene and tetrahydrofuran. The mass percentage concentration of the rubber solution is preferably 5-40%, and specifically can be 5%, 10%, 15%, 20%, 25%, 30%, 35% and 40%.
In some embodiments of the invention, the process of providing the rubber solution in step a) is as follows: dissolving natural rubber and trans-1, 4-butadiene-isoprene copolymer rubber in a solvent to obtain a rubber solution. In other embodiments of the present invention, the process of providing the rubber solution in step a) is as follows: adopting a bulk polymerization process to synthesize the trans-1, 4-butadiene-isoprene rubber glue solution. In other embodiments of the present invention, the process of providing the rubber solution in step a) is as follows: providing bulk polymerization trans-1, 4-butadiene-isoprene rubber glue solution; dissolving cis-1, 4-polyisoprene rubber in a solvent to obtain a rubber solution; and mixing the bulk polymerization trans-1, 4-butadiene-isoprene rubber glue solution with the rubber dissolving solution to obtain a rubber solution.
[ regarding step b ]:
b) Mixing the rubber solution provided in the step a) with an auxiliary agent or an auxiliary agent suspension to obtain a mixed solution.
In the invention, the addition mode of the auxiliary agent can be directly adding the auxiliary agent, or can be adding in the form of an auxiliary agent suspension (namely, the auxiliary agent is prepared into a suspension in advance and then used).
In the present invention, the auxiliary preferably includes, based on 100 parts by mass of the rubber in the rubber solution provided in step a):
wherein:
the reinforcing agent is preferably one or more of carbon black, white carbon black, argil, calcium carbonate, graphene and carbon nanotubes. The reinforcing agent is 10-120 parts, specifically 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts and 120 parts.
The amount of the zinc oxide is 0-8 parts, and specifically can be 0 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts and 8 parts.
The usage amount of the stearic acid is 0-4 parts, specifically 0 part, 1 part, 2 parts, 3 parts and 4 parts.
The anti-aging agent is preferably one or more of anti-aging agent 4020, anti-aging agent RD, anti-aging agent 4010NA, anti-aging agent AW, anti-aging agent 4030 and microcrystalline wax. The anti-aging agent is 0-6 parts, specifically 0 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts and 6 parts.
The coupling agent is a silane coupling agent, preferably one or more of silane coupling agents of Si-69, si-75, KH550, KH560 and KH 570. The amount of the coupling agent is 0.1-8.0 parts, specifically 0.1 part, 0.5 part, 1.0 part, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, 4.5 parts, 5.0 parts, 5.5 parts, 6.0 parts, 6.5 parts, 7.0 parts, 7.5 parts, 8.0 parts.
The plasticizer is preferably one or more of aromatic oil, paraffinic oil and naphthenic oil. The aromatic oil is preferably an environmentally friendly aromatic oil. The amount of the plasticizer is 0 to 15 parts, and specifically may be 0 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts and 15 parts.
The scorch retarder is preferably the scorch retarder CTP. The dosage of the scorch retarder is 0 to 0.4 part, and specifically can be 0 part, 0.1 part, 0.2 part, 0.3 part and 0.4 part.
In the present invention, the auxiliary suspension is a suspension in which an auxiliary is dispersed in a dispersion medium. The kind of the auxiliary agent is the same as that in the technical scheme, and is not described again here. The dispersion medium is preferably one or more of n-heptane, n-hexane, cyclohexane, toluene, xylene, and tetrahydrofuran. In the auxiliary agent suspension, the dosage ratio of the auxiliary agent to the dispersing medium is preferably (10-100) g to (50-1000) mL.
In the present invention, the mixing of the rubber solution provided in step a) with the adjuvant/adjuvant suspension is preferably carried out by shear mixing, in particular by means of a propeller stirrer. In the present invention, the conditions of the shear mixing are preferably: the speed is 1000 r/min, and the time is 30min. After mixing, a mixed solution is obtained.
[ with respect to step c ]:
c) And removing the solvent from the mixed solution to obtain a master batch matrix.
In the present invention, the solvent removal method is not particularly limited, and may be a conventional method in the art, such as drying, vacuum pumping, or supercritical method. In the process of removing the solvent, if the system contains unreacted monomers, the unreacted monomers are also removed. And removing the solvent to obtain a master batch matrix.
[ with respect to step d ]:
d) Mixing and banburying rubber, an accelerator, sulfur and an auxiliary agent to obtain rubber master batch.
In the present invention, the rubber comprises the masterbatch base; the mass percentage of the master batch matrix in the rubber is 14-100%, and specifically can be 14%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%. That is, the rubber may be the whole of the matrix of the masterbatch obtained in step c) or may be a mixture of the matrix of the masterbatch obtained in step c) with another rubber. Among them, the other rubber is preferably natural rubber and/or butadiene-styrene rubber. When the mass ratio percentage is not 100 percent, namely when a part of the master batch matrix is introduced into other rubber, compared with the total adoption of other rubber, the mechanical property and the wear resistance of the material can be effectively improved, and the compression heat generation and the rolling resistance are reduced; that is, when a part of the master batch base is introduced into rubber, the performance of the rubber material can be improved. When the mass ratio percentage is 100%, namely the matrix is the matrix of the wet masterbatch obtained in the step c), compared with the dry masterbatch process, the dry masterbatch process can effectively improve the mechanical property and the wear resistance of the material, and reduce the compression heat generation and the rolling resistance.
In the present invention, the accelerator is preferably one or more of accelerator NS, accelerator CBS, accelerator DPG, accelerator NOBS, accelerator TMTD and accelerator D.
In the invention, the amount of the accelerator is preferably 1.0-2.5 parts, specifically 1.0 part, 1.5 parts, 2.0 parts and 2.5 parts, based on 100 parts by mass of the rubber in the rubber solution provided in the step a); the preferable amount of the sulfur is 1.0-2.5 parts, and specifically 1.0 part, 1.5 parts, 2.0 parts and 2.5 parts.
In the invention, the auxiliary agent in the step d) comprises the following components in parts by mass based on 100 parts by mass of the rubber in the rubber solution provided in the step a):
wherein:
the dosage of the zinc oxide is 0 to 8 parts, and specifically can be 0 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts and 8 parts.
The usage amount of the stearic acid is 0-4 parts, specifically 0 part, 1 part, 2 parts, 3 parts and 4 parts.
The selection range of the types of the anti-aging agents is consistent with that in the technical scheme, and is not repeated herein. The amount of the anti-aging agent is 0-6 parts, specifically 0 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts and 6 parts.
The selection range of the plasticizer is the same as that in the above technical solution, and the details are not repeated herein. The amount of the plasticizer is 0 to 15 parts, and specifically may be 0 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts and 15 parts.
The selection range of the kind of the scorch retarder is consistent with that in the technical scheme, and is not repeated herein. The dosage of the scorch retarder is 0 to 0.4 part, and specifically can be 0 part, 0.1 part, 0.2 part, 0.3 part and 0.4 part.
The amount of the carbon black is 0-60 parts, and specifically can be 0 part, 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 55 parts and 60 parts.
In the present invention, the auxiliary in step b) contains 7 components, wherein 2 components (reinforcing agent and coupling agent) are used in amounts other than 0 as essential components, and the other 5 components are not essential components. The auxiliary agent in the step d) contains 6 components, the using amount of each component can be 0, and the components are unnecessary components; the other 5 components except carbon black correspond to 5 optional components in the auxiliary agent in the step b) and are similar components, for example, zinc oxide is contained in the auxiliary agent in the step b), zinc oxide is also contained in the auxiliary agent in the step d), and the zinc oxide and the auxiliary agent are similar components.
In the present invention, the amounts of the auxiliary agents of the same type as those used in the auxiliary agents of step b) and step d) are not 0 at the same time, preferably not 0 at the same time, except for the plasticizer and the scorch retarder. The meanings are illustrated below: for example, for zinc oxide, if the amount used in step b) is 0, the amount used in step d) cannot be 0; if the dosage in the step d) is 0, the dosage in the step b) cannot be 0; i.e. for the same component zinc oxide, it is added in one of the steps b) and d), i.e. the auxiliary component can be added both in step b) and in step d). Other components are not listed and so on. In the present invention, the above-mentioned components of the same type do not contain a plasticizer and a scorch retarder, i.e., the plasticizer and the scorch retarder do not comply with the above-mentioned limitations, and 3 components of the same type of auxiliary agents other than the plasticizer and the scorch retarder (i.e., zinc oxide, stearic acid, and antioxidant) comply with the above-mentioned limitations, and therefore, the amount of the plasticizer used in step b) and step d) can be 0 at the same time, i.e., the plasticizer is not added, and the scorch retarder is also the same.
In the present invention, when one of the auxiliary components is other than 0 in step b) or step d), it is preferable to use the following amounts, respectively: the using amount of the zinc oxide is 3-8 parts, and specifically can be 3 parts, 4 parts, 5 parts, 6 parts, 7 parts and 8 parts. The usage amount of stearic acid is 1-4 parts, specifically 1 part, 2 parts, 3 parts and 4 parts. The using amount of the anti-aging agent is 1 to 6 parts, and specifically can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts and 6 parts.
In the invention, the mixing and banburying of the rubber, the accelerator, the sulfur and the auxiliary agent are preferably carried out at 50-110 ℃, the rotation speed of the banbury mixer is preferably 30-80 r/min, and the banburying time is preferably 0.5-2 min. And (3) banburying, discharging rubber, and discharging rubber sheets through an open mill to obtain final rubber, namely the rubber master batch.
In the present invention, after the final rubber compound is obtained, it is preferably left at room temperature for one day and then vulcanized. In the invention, the vulcanization temperature is preferably 140-170 ℃, and the vulcanization time is preferably plus process vulcanization time +5min. And vulcanizing to obtain vulcanized rubber.
The invention also provides the rubber master batch prepared by the preparation method in the technical scheme.
According to the preparation method provided by the invention, the high-performance rubber masterbatch is prepared by adopting a wet method, compared with the dry method masterbatch, the filler dispersibility is greatly improved, and better associativity is formed between the filler and other components, so that the vulcanized rubber obtained after vulcanization has excellent mechanical property and wear resistance, and the rolling resistance and heat generation are effectively reduced; can be applied to the fields of tires, damping elastic elements, rubber belts and the like.
The experimental result shows that the tensile strength of the rubber product obtained by the invention is more than 26MPa, the tear strength is more than 96KN/m, the rebound resilience is more than 52 percent, the compression heat generation is below 40 ℃, the rolling resistance tan delta @60 ℃ is below 0.215, and the DIN abrasion is 99mm 3 Less than 40m, excellent mechanical property and wear resistance, and lower compression heat generation and rolling resistance.
For a further understanding of the present invention, reference will now be made to the following preferred embodiments of the invention in conjunction with the examples, but it is to be understood that the description is intended to further illustrate the features and advantages of the invention and is not intended to limit the scope of the claims which follow.
The materials mainly used in the following examples and comparative examples are as follows: natural rubber: designation SCRWF, marine glue group. Synthetic cis-1, 4-polyisoprene rubber: the designation SKI-3, is that isoprene monomer is prepared by solution polymerization production process, russian N factory. Synthesis of trans-1, 4-butadiene-isoprene rubber: the TBIR 2249 is prepared by a bulk polymerization production process for butadiene monomers and isoprene monomers, and is available from Shandong Hua Polymer materials Co. The carbon black used in the formula is purchased from American cabot company, the white carbon black is purchased from Solvay fine chemical additives (Qingdao) Co., ltd, and other raw materials and auxiliary agents are all commercial products. The scorch retarder is CTP.
Example 1
a) Providing a rubber solution, specifically as follows:
90 parts of natural rubber and 10 parts of trans-1, 4-butadiene-isoprene rubber were dissolved in 1250mL of n-heptane to prepare a rubber solution having a concentration of 8%.
b) The auxiliary agent is added into the rubber solution (containing 100 parts of rubber), and the mixture is fully sheared and mixed to obtain the mixed solution.
Wherein, the auxiliary agent comprises:
c) And (3) removing the n-heptane solvent in the mixed solution to obtain the master batch matrix.
d) Banburying: the master batch matrix, 1.0 part of accelerator NS and 1.5 parts of sulfur are put into an internal mixer (temperature 50 ℃, 50 r/min) and are mixed for 1.5min for rubber discharge. And (3) discharging the mixed rubber discharged from the internal mixer through an open mill to obtain final rubber, standing for one day at room temperature to obtain the rubber masterbatch.
Example 2
a) Providing a rubber solution, specifically as follows:
the trans-1, 4-butadiene-isoprene rubber glue solution is synthesized by adopting a bulk polymerization process, the concentration of the glue solution is 20 percent, and the rest is unreacted monomers.
80 parts of synthetic cis-1, 4-polyisoprene rubber was dissolved in 800mL of n-heptane to prepare a rubber solution having a concentration of 10%.
Mixing the trans-1, 4-butadiene-isoprene rubber glue solution with a rubber dissolving solution (the mass ratio of the trans-1, 4-butadiene-isoprene rubber to the cis-1, 4-polyisoprene rubber is 20: 80) to obtain a rubber solution.
b) The adjuvant was dispersed in 500mL of n-heptane to give an adjuvant suspension. The aid suspension was added to the above rubber solution (containing 100 parts of rubber), and sufficiently sheared and mixed to obtain a mixed solution.
Wherein, the auxiliary agent comprises:
c) Removing the n-heptane solvent from the mixed solution to obtain the master batch matrix.
d) Banburying: in the same manner as in example 1, a rubber master batch was obtained.
Example 3
a) Providing a rubber solution, specifically as follows:
adopting a bulk polymerization process to synthesize trans-1, 4-butadiene-isoprene rubber glue solution, wherein the concentration of the glue solution is 10 percent, and the rest is unreacted monomer.
b) The auxiliary agent is added into the rubber solution (containing 100 parts of rubber), and the mixture is fully sheared and mixed to obtain a mixed solution.
Wherein, the auxiliary agent comprises:
50 parts of white carbon black reinforcing agent;
5.0 parts of silane coupling agent Si-69.
c) And (4) removing volatile components in the mixed solution to obtain a master batch matrix.
d) Banburying: 15.5 parts of master batch matrix, 80 parts of natural rubber, 10 parts of butadiene-styrene rubber, 1.0 part of accelerator NS, 1.5 parts of sulfur and an auxiliary agent are put into an internal mixer (the temperature is 50 ℃ and the speed is 50 r/min) and are mixed for 1.5min for rubber discharge. And (3) discharging the mixed rubber discharged from the internal mixer through an open mill to obtain final rubber, standing for one day at room temperature to obtain the rubber masterbatch.
Wherein, the auxiliary agent comprises:
example 4
a) The method comprises the following steps The same as in example 3.
b) The method comprises the following steps The same as in example 3.
c) The method comprises the following steps The same as in example 3.
d) Banburying: 31 parts of master batch matrix, 80 parts of natural rubber, 1.0 part of accelerator NS, 1.5 parts of sulfur and auxiliary agent (same as example 3) are put into an internal mixer (temperature 50 ℃, 50 r/min) and are mixed for 1.5min for rubber discharge. And (3) discharging the mixed rubber discharged from the internal mixer through an open mill to obtain final rubber, standing for one day at room temperature to obtain the rubber masterbatch.
Comparative example 1
1. Raw materials:
80 parts of natural rubber, 20 parts of butadiene-styrene rubber, 3.0 parts of zinc oxide, 2.0 parts of stearic acid, 2.0 parts of an anti-aging agent 402, 1.0 part of an anti-aging agent RD, 2.0 parts of microcrystalline wax, 55 parts of carbon black N220, 10.0 parts of environment-friendly aromatic oil, 1.0 part of an accelerator NS, 1.5 parts of sulfur and 0.2 part of a scorch retarder.
2. Preparation:
s1, first-stage banburying:
an internal mixer (the temperature is 70 ℃ and 70 r/min), firstly adding rubber for internal mixing for 1min, then adding zinc oxide, stearic acid, an anti-aging agent, carbon black, microcrystalline wax, environment-friendly aromatic oil and an anti-scorching agent, continuously internal mixing for 2min, then cleaning a top plug, and totally internal mixing for 5 rubber discharges; and (3) discharging the rubber compound discharged from the internal mixer through an open mill to obtain a section of master batch, and standing at room temperature for 2 hours.
S2, two-stage banburying:
and (3) putting the primary rubber batch, the accelerator and the sulfur into an internal mixer (the temperature is 50 ℃ and the speed is 50 r/min), and carrying out internal mixing for 1.5min to discharge rubber. And discharging the mixed rubber discharged from the internal mixer through an open mill to obtain final mixed rubber, and standing for one day at room temperature.
Example 5: performance test
The master batches obtained in the comparative example 1 and the examples 1 to 4 were vulcanized (the vulcanization temperature was 150 ℃ and the vulcanization time was the process positive vulcanization time +5 min) to obtain vulcanized rubber samples. Various performance tests were performed on the vulcanizate samples.
The equipment and the test method used in the performance test are shown in table 1, and the test results are shown in table 2.
Table 1: apparatus and test method for use
| Item | Adopted equipment | Standards/methods used |
| Filler dispersancy | GT-505-CBD (high speed railway company) | / |
| Tensile strength | Z005 type electronic tension tester (Zwick company) | GB/T 528-2009 |
| Tear performance | Z005 type electronic tension tester (Zwick company) | GB/T 529-2008 |
| Heat generation by compression | RH-2000 type compression heat generation tester (high-speed railway company) | Temperature 55 ℃ and load 1MPa |
| Resilience performance | Impact elasticity tester (high-speed rail company) | GB/T 1681-2009 |
| DIN abrasion | GT-7012-D Shao Bo Er abrasion tester (high speed railway company) | GB/T 9867-2008 |
| Rolling resistance tan delta @60 deg.C | 861 e Dynamic thermomechanical property analyzer (Mettler corporation) | Frequency 10Hz, strain 5% |
Table 2: test results
As can be seen from the test results in Table 2, the rubber products obtained in the examples of the present invention have a tensile strength of 26MPa or more, a tear strength of 96KN/m or more, a rebound resilience of 52% or more, a heat generation by compression of 40 ℃ or less, a rolling resistance tan delta @60 ℃ of 0.215 or less, and a DIN abrasion of 99mm 3 Less than 40m, excellent mechanical property and wear resistance, and lower compression heat generation and rolling resistance.
Compared with examples 3-4, the samples obtained in comparative example 1 have reduced mechanical properties (the reduction of tear strength is more than 3 units, the reduction of resilience is more than 6 units), increased heat generation by compression (the increase is more than 3.6 ℃), increased rolling resistance (the increase is more than 16%), and poor wear resistance (the wear volume is increased by more than 7%). The invention proves that the mechanical property and the wear resistance of the material can be improved, and the compression heat generation and the rolling resistance can be reduced after the wet master batch product prepared by the wet process is added into the natural rubber/butadiene-styrene rubber blended rubber.
In examples 1-4, the comprehensive properties of the products obtained in examples 1-2 are further significantly improved, and it is proved that the mechanical properties and wear resistance of the material can be effectively improved, and the heat generation by compression and rolling resistance can be reduced by using the master batch product prepared by the wet process as the base rubber alone.
The foregoing examples are provided to facilitate an understanding of the principles of the invention and their core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, it is possible to make various improvements and modifications to the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. The preparation method of the rubber master batch is characterized by comprising the following steps:
a) Providing a rubber solution, specifically as follows:
dissolving rubber in a solvent to obtain a rubber dissolving solution;
or
II, providing a bulk polymerization rubber glue solution;
or
Mixing the rubber dissolving solution with the bulk polymerization rubber glue solution to obtain a rubber mixed solution;
b) Mixing the rubber solution provided in the step a) with an auxiliary agent or an auxiliary agent suspension to obtain a mixed solution;
c) Removing the solvent from the mixed solution to obtain a master batch matrix;
d) Mixing and banburying rubber, an accelerator, sulfur and an auxiliary agent to obtain rubber master batch;
the rubber comprises the masterbatch matrix; the mass percentage of the master batch matrix in the rubber is 14-100%;
wherein the content of the first and second substances,
in the i, the rubber is synthetic rubber or synthetic rubber and natural rubber; wherein the synthetic rubber is formed by taking at least one of butadiene monomer, isoprene monomer and styrene monomer as raw materials;
in the ii, the rubber in the bulk polymerization rubber glue solution is formed by taking at least one of a butadiene monomer, an isoprene monomer and a styrene monomer as a raw material;
in the iii, the rubber in the bulk polymerization rubber cement is formed by taking at least one of a butadiene monomer, an isoprene monomer and a styrene monomer as a raw material; the rubber in the rubber dissolving liquid is synthetic rubber or synthetic rubber and natural rubber, and is different from the rubber in the bulk polymerization rubber liquid.
2. The method according to claim 1, wherein in the i, the rubber is trans-1, 4-butadiene-isoprene copolymer rubber or trans-1, 4-butadiene-isoprene copolymer rubber and natural rubber;
in the ii, the bulk polymerization rubber cement is bulk polymerization trans-1, 4-butadiene-isoprene rubber cement;
in the iii, the bulk polymerization rubber cement is bulk polymerization trans-1, 4-butadiene-isoprene rubber cement; the rubber in the rubber solution is other rubber except the trans-1, 4-butadiene-isoprene copolymer rubber, and the other rubber is natural rubber or cis-1, 4-polyisoprene rubber.
3. The preparation method according to claim 1, wherein the rubber solution provided in the step a) has a mass percentage concentration of 5-40%.
4. The method according to claim 1, wherein the auxiliary in step b) comprises, based on 100 parts by mass of the rubber in the rubber solution provided in step a):
wherein the content of the first and second substances,
the reinforcing agent is one or more of carbon black, white carbon black, argil, calcium carbonate, graphene and carbon nano tubes;
the coupling agent is a silane coupling agent;
based on 100 parts by mass of the rubber in the rubber solution provided in the step a), the auxiliary agent in the step d) comprises:
besides the plasticizer and the scorch retarder, the dosage of the auxiliary agent in the step d) and the same type of components in the auxiliary agent in the step b) is not 0 at the same time.
5. The method according to claim 4, wherein the silane coupling agent is one or more of silane coupling agents Si-69, si-75, KH550, KH560 and KH 570.
6. The preparation method according to claim 4, wherein the antioxidant is selected from one or more of antioxidant 4020, antioxidant RD, antioxidant 4010NA, antioxidant AW, antioxidant 4030 and microcrystalline wax;
the plasticizer is selected from one or more of aromatic oil, paraffin oil and naphthenic oil;
the scorch retarder is the scorch retarder CTP.
7. The method according to claim 1, wherein the mass ratio of the synthetic rubber in the mixed rubber of the synthetic rubber and the natural rubber in the i is 5 to 50%.
8. The method according to claim 1, wherein in the i, the solvent is selected from one or more of n-heptane, n-hexane, cyclohexane, toluene, xylene, and tetrahydrofuran;
in the iii, the solvent in the rubber dissolving liquid is selected from one or more of n-heptane, n-hexane, cyclohexane, toluene, xylene and tetrahydrofuran;
in the step b), the dispersion medium in the auxiliary agent suspension is selected from one or more of n-heptane, n-hexane, cyclohexane, toluene, xylene and tetrahydrofuran;
in the assistant suspension, the dosage ratio of the assistant to the dispersion medium is (10-100) g to (50-1000) mL.
9. The process of claim 1, wherein in step D), the accelerator is selected from one or more of accelerator NS, accelerator CBS, accelerator DPG, accelerator NOBS, accelerator TMTD and accelerator D;
based on 100 parts by mass of rubber in the rubber solution provided by the step a), the using amount of the accelerator is 1.0-2.5 parts, and the using amount of the sulfur is 1.0-2.5 parts.
10. A rubber master batch obtained by the production method as claimed in any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN115926207A (en) * | 2022-11-23 | 2023-04-07 | 辽宁维航基业科技有限公司 | Preparation method of soft wear-resistant glue |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327315A (en) * | 2014-11-03 | 2015-02-04 | 怡维怡橡胶研究院有限公司 | Application of continuously-prepared rubber masterbatch in car tire base rubber |
| 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 |
| CN114907590A (en) * | 2022-05-31 | 2022-08-16 | 山东华聚高分子材料有限公司 | Synthetic rubber wet masterbatch and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN104327315A (en) * | 2014-11-03 | 2015-02-04 | 怡维怡橡胶研究院有限公司 | Application of continuously-prepared rubber masterbatch in car tire base rubber |
| CN114907590A (en) * | 2022-05-31 | 2022-08-16 | 山东华聚高分子材料有限公司 | Synthetic rubber wet masterbatch and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115926207A (en) * | 2022-11-23 | 2023-04-07 | 辽宁维航基业科技有限公司 | Preparation method of soft wear-resistant glue |
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