CN115340632A - Modified styrene-butadiene rubber and preparation method and application thereof - Google Patents
Modified styrene-butadiene rubber and preparation method and application thereof Download PDFInfo
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- CN115340632A CN115340632A CN202110519146.7A CN202110519146A CN115340632A CN 115340632 A CN115340632 A CN 115340632A CN 202110519146 A CN202110519146 A CN 202110519146A CN 115340632 A CN115340632 A CN 115340632A
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- styrene
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- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 81
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 84
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 26
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 22
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 18
- 208000012839 conversion disease Diseases 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 52
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 33
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 239000003792 electrolyte Substances 0.000 claims description 21
- 239000011790 ferrous sulphate Substances 0.000 claims description 19
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 19
- 239000003292 glue Substances 0.000 claims description 19
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 18
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000000344 soap Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- ODHYIQOBTIWVRZ-UHFFFAOYSA-N n-propan-2-ylhydroxylamine Chemical group CC(C)NO ODHYIQOBTIWVRZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical group CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 6
- 230000015271 coagulation Effects 0.000 claims description 5
- 238000005345 coagulation Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical group CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 claims description 3
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims 2
- 238000005520 cutting process Methods 0.000 abstract description 20
- 229920001971 elastomer Polymers 0.000 abstract description 12
- 239000005060 rubber Substances 0.000 abstract description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- CFJYNSNXFXLKNS-UHFFFAOYSA-N p-menthane Chemical compound CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical group CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- QUPCNWFFTANZPX-UHFFFAOYSA-N hydrogen peroxide;1-methyl-4-propan-2-ylcyclohexane Chemical compound OO.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 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 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NVJCKICOBXMJIJ-UHFFFAOYSA-M potassium;1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [K+].C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C([O-])=O NVJCKICOBXMJIJ-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010091 synthetic rubber production Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
-
- 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
- C08L9/06—Copolymers with styrene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides modified styrene-butadiene rubber and a preparation method and application thereof. The preparation method comprises the following steps: s1, preparing a raw material liquid comprising a first part of styrene, butadiene, an emulsifier, a reducing agent and water, and adding an initiator into the raw material liquid to perform emulsion polymerization; and S2, adding a second part of styrene into the emulsion polymerization reaction system and continuing to react when the reaction conversion rate reaches 10-12%, and stopping the reaction when the reaction conversion rate reaches 60% so as to obtain the modified styrene-butadiene rubber. The preparation method can realize the effective control of the weight content and the Mooney viscosity of the styrene unit in the modified styrene-butadiene rubber, and promote the weight content of the styrene unit to reach 38-42 percent and the Mooney viscosity (ML) 1+4 100℃ ) 55 to 65 percent, thereby greatly improving the cutting resistance of the rubberCan better meet the requirements of rubber seeds for engineering tires.
Description
Technical Field
The invention relates to the technical field of synthetic rubber production, and particularly relates to modified styrene-butadiene rubber as well as a preparation method and application thereof.
Background
In recent years, with the rapid development of the engineering machinery industry in China, the prosperous mining industry and the prosperous urban engineering construction, the engineering tire serving as one wing of the tire is rapidly developed all over the world, the demand of the engineering tire is more and more large, and the engineering tire becomes one of the fastest and largest tire markets. The engineering tire yield accounts for 1% of the total tire yield, but the glue consumption can reach more than 15%, and the engineering tire yield becomes one of industries with far higher added values than automobile tires. The engineering tire is a low-speed tire, is mainly operated in a mining area, has a complex environment, inevitably contacts various broken stones and sharp ore blocks, cuts and damages the tire, and easily causes the tire tread to collapse and fall blocks. Moreover, the large agricultural tire is mainly matched with a high-horsepower tractor, and the tire is inevitably punctured and pricked due to crop root stubble remained after being harvested in a cultivated land in actual use. Therefore, the service quality of the engineering mining tire and the large agricultural tire is improved, and the key point is to improve the cutting resistance and puncture resistance of the tire.
The patent CN201810026700.6 relates to a special tire base rubber composition for engineering machinery tires, which comprises raw materials based on 100 parts by weight of natural rubber, 35-45 parts by weight of carbon black N330, 0-6 parts by weight of white carbon black, 1.0-3.0 parts by weight of stearic acid, 2.0-5.0 parts by weight of zinc oxide, 0.7-1.0 part by weight of N-tert-butyl-2-benzothiazole sulfonamide, 1.5-2.5 parts by weight of sulfur, and 0.5-1.0 part by weight of antioxidant 4020,0.5-1.5 parts by weight of antioxidant RD. Patent CN200820026043.7 discloses a deep-pattern high-puncture-resistant cutting-resistant oblique-crossing giant engineering tire, which comprises a tire body composed of a plurality of layers of high-strength fiber cord fabrics, wherein the outer side of the tire body is fixedly connected with a tire tread composed of tire tread rubber, a plurality of layers of steel wire buffer layers composed of steel wire cord fabrics are arranged between the tire tread and the tire body, the tire tread strength is increased, the impact force of the tire on the ground is absorbed, the adhesive force between the tire tread rubber and the tire body can also be increased, and the puncture resistance and puncture resistance of the tire on sharp objects are effectively improved. To sum up, the research on engineering tires at home and abroad is mainly focused on improving the cutting resistance and puncture resistance of the tires by developing processing application formulas, and little modification is performed on rubber materials.
Styrene Butadiene Rubber (SBR) is one of important Synthetic Rubber (SR) varieties, and is a general synthetic rubber with the highest yield and the highest consumption in the world at present. In particular, the styrene butadiene rubber can be widely applied to the manufacture of engineering tires due to the excellent mechanical property of the styrene butadiene rubber. However, when the styrene butadiene rubber in the prior art is applied to the field of engineering tires, the cutting resistance is poor, and the application requirement of rubber materials of the engineering tires cannot be met.
Disclosure of Invention
The invention mainly aims to provide a modified styrene-butadiene rubber, and a preparation method and application thereof, so as to solve the problem of poor cutting resistance when the styrene-butadiene rubber is applied to the field of engineering tires in the prior art.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing a modified styrene-butadiene rubber. The preparation method comprises the following steps: s1, preparing a raw material liquid comprising a first part of styrene, butadiene, an emulsifier, a reducing agent and water, and adding an initiator into the raw material liquid to carry out emulsion polymerization reaction; wherein, the raw material liquid comprises 40 to 47 weight portions of first part styrene, 48 to 56 weight portions of butadiene, 4.0 to 5.5 weight portions of emulsifier, 0.065 to 0.085 weight portion of reducing agent and 180 to 200 weight portions of water, and the weight portion of the initiator is 0.06 to 0.12 weight portion; and S2, adding a second part of styrene into the emulsion polymerization reaction system and continuing to react when the reaction conversion rate reaches 10-12%, and stopping the reaction when the reaction conversion rate reaches 60% so as to obtain the modified styrene-butadiene rubber.
Furthermore, the weight ratio of the second part of styrene to the first part of styrene is 1 (3-6).
Further, the raw material liquid comprises 42 to 45 parts by weight of styrene, 50 to 54 parts by weight of butadiene, 4.5 to 5.0 parts by weight of emulsifier, 0.065 to 0.085 part by weight of reducing agent and 180 to 200 parts by weight of water; and the initiator accounts for 0.06-0.12 part by weight.
Furthermore, the raw material liquid also comprises 0.07 to 0.15 part of molecular weight regulator and 0.63 to 1.03 part of electrolyte according to the parts by weight.
Further, step S1 includes: carrying out vacuum and nitrogen replacement on a polymerization kettle, adding all raw materials into the polymerization kettle to form a raw material liquid, reducing the temperature in the polymerization kettle to be below 5 ℃, and then adding an initiator into the raw material liquid to carry out emulsion polymerization. The step S2 comprises the following steps: adding a terminator into the polymerization kettle to terminate the reaction when the reaction conversion rate reaches 60 percent to obtain a polymerization glue solution; and adding the polymerized glue solution into a dilute sulfuric acid solution for coagulation, washing and drying to obtain the modified styrene-butadiene rubber.
Further, the emulsifier is disproportionated potassium rosinate soap and/or fatty acid sodium soap.
Preferably, the initiator is p-menthane hydroperoxide and/or diisopropylbenzene hydroperoxide.
Preferably, the reducing agent comprises one or more of ferrous sulfate, sodium formaldehyde sulfoxylate and ethylenediaminetetraacetic acid tetrasodium salt; the preferable reducing agent comprises ferrous sulfate, sodium formaldehyde sulfoxylate and ethylenediaminetetraacetic acid tetrasodium salt, and the weight ratio of the ferrous sulfate, the sodium formaldehyde sulfoxylate and the ethylenediaminetetraacetic acid tetrasodium salt is 1 (3-5) to 2.5.
Further, the molecular weight regulator is tertiary dodecyl mercaptan and/or n-dodecyl mercaptan.
Preferably, the electrolyte comprises one or more of phosphoric acid, potassium hydroxide, ethylenediaminetetraacetic acid tetrasodium salt and sodium m-methine-dinaphthalenesulfonate; the preferable electrolyte comprises phosphoric acid, potassium hydroxide, ethylene diamine tetraacetic acid tetrasodium salt and sodium m-methine dinaphthalene sulfonate, and the weight ratio of the four is (20-30): (30-50): 3: (10-20).
Further, the terminator is isopropyl hydroxylamine and/or sulfate; preferably, the amount of the terminating agent is 0.055-0.150% by weight of the emulsifier.
According to another aspect of the present invention, there is provided a modified styrene-butadiene rubber prepared by the above-mentioned preparation method.
Furthermore, the weight content of the styrene unit in the modified styrene-butadiene rubber is 38-42 percent; the Mooney viscosity of the modified styrene-butadiene rubber is 55-65.
According to another aspect of the invention, the modified styrene-butadiene rubber prepared by the preparation method is provided for application as a material for manufacturing engineering tires.
The preparation method can realize the effective control of the weight content and the Mooney viscosity of the styrene unit in the modified styrene-butadiene rubber, and promote the weight content of the styrene unit to reach 38-42 percent and the Mooney viscosity (ML) 1+4 100℃ ) 55-65, thereby greatly improving the cutting resistance of the rubber and better meeting the requirements of rubber seeds for engineering tires.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background section, styrene-butadiene rubber in the prior art has poor cut resistance when applied to the field of engineering tire manufacturing. In order to solve the problem, the invention provides a preparation method of modified styrene-butadiene rubber, which comprises the following steps: s1, preparing a raw material liquid comprising a first part of styrene, butadiene, an emulsifier, a reducing agent and water, and adding an initiator into the raw material liquid to perform emulsion polymerization. And S2, adding a second part of styrene into the emulsion polymerization reaction system and continuing to react when the reaction conversion rate reaches 10-12%, and stopping the reaction when the reaction conversion rate reaches 60% so as to obtain the modified styrene-butadiene rubber. Wherein the raw material liquid comprises 40 to 47 parts by weight of first part styrene, 48 to 56 parts by weight of butadiene, 4.0 to 5.5 parts by weight of emulsifier, 0.065 to 0.085 part by weight of reducing agent and 180 to 200 parts by weight of water, and the weight part of the initiator is 0.06 to 0.12 part by weight.
The invention uses each component in the raw material liquidThe amount is controlled within the range, so that the synergistic effect of each component can be better exerted, and the weight content of the styrene unit in the obtained modified styrene-butadiene rubber is more appropriate and reaches 38-42 percent. Particularly, the invention firstly adds a part of styrene and butadiene for emulsion polymerization reaction, when the reaction conversion rate reaches 10-12%, then adds a second part of styrene into the reaction system of emulsion polymerization and continues the reaction until the conversion rate reaches 60%, and then the reaction is terminated. This allows the viscosity of the polymerization system to be controlled to a more suitable Mooney viscosity level, mooney viscosity (ML) 1+4 100℃ ) Reaches 55 to 65. The two reasons realize the weight content of the styrene unit in the modified styrene-butadiene rubber and the controllability of the Mooney viscosity of the modified styrene-butadiene rubber, and finally effectively improve the cutting resistance of the styrene-butadiene rubber. Meanwhile, the method provided by the invention has the advantages that the emulsion polymerization reaction is more stable, so that the preparation process of the modified styrene-butadiene rubber is more stable, the prepared modified styrene-butadiene rubber has more uniform performance, and the method has the comprehensive advantages of other styrene-butadiene rubbers besides better cutting resistance.
In a word, the modified styrene-butadiene rubber obtained by the preparation method has the weight content of styrene units of 38-42 percent, the Mooney viscosity of 55-65 percent, and the cutting resistance improved by more than 25 percent compared with the traditional styrene-butadiene rubber, thereby being an ideal rubber for engineering tires.
Preferably, the weight ratio of the second part of styrene to the first part of styrene is 1 (3-6). Within the range, the viscosity of the polymerization system can be further controlled to be a more appropriate viscosity level, so that the stability of the polymerization reaction is better, the weight content of styrene units in the modified styrene-butadiene rubber and the Mooney viscosity of the modified styrene-butadiene rubber can be more effectively controlled, and the modified styrene-butadiene rubber with better cutting resistance can be prepared.
In a preferred embodiment, the raw material liquid comprises 42 to 45 parts of styrene, 50 to 54 parts of butadiene, 4.5 to 5.0 parts of an emulsifier, 0.065 to 0.085 parts of a reducing agent, and 180 to 200 parts of water; and the weight portion of the initiator is 0.06-0.12 portion. Within the range, the synergistic effect of the components is better, so that the weight content of styrene units in the obtained modified styrene-butadiene rubber is better, the Mooney viscosity of the modified styrene-butadiene rubber is better, and the cutting resistance of the modified styrene-butadiene rubber is further improved.
Preferably, step S1 comprises: carrying out vacuum and nitrogen replacement on a polymerization kettle, adding all raw materials into the polymerization kettle to form a raw material liquid, reducing the temperature in the polymerization kettle to be below 5 ℃, and then adding an initiator into the raw material liquid to carry out emulsion polymerization. By doing so, the raw material liquid can be made uniform and then the initiator can be added for polymerization, which is beneficial to maintaining the stability of the polymerization reaction. The step S2 comprises the following steps: and when the reaction conversion rate reaches 60%, adding a terminator into the polymerization kettle to terminate the reaction, thereby obtaining the polymerization glue solution. And adding the polymerized glue solution into a dilute sulfuric acid solution for coagulation, washing and drying to obtain the modified styrene-butadiene rubber. Specifically, the polymerization glue solution is added into a dilute sulfuric acid solution with the concentration of 0.5%, stirring is carried out, and the temperature is controlled at 60 ℃ for coagulation, so that the coagulation of the polymerization glue solution can be promoted to be more complete, and the performance of the obtained modified styrene-butadiene rubber is more uniform.
The purpose of making the polymerization reaction more stable and the reaction efficiency higher is based on. Preferably, the emulsifier is disproportionated potassium rosinate soap and/or fatty acid sodium soap. Preferably the initiator is p-menthane hydroperoxide and/or diisopropylbenzene hydroperoxide. Preferably the reducing agent comprises one or more of ferrous sulphate, sodium formaldehyde sulfoxylate and ethylenediaminetetraacetic acid tetrasodium salt. More preferably, the reducing agent comprises ferrous sulfate, sodium formaldehyde sulfoxylate and ethylenediaminetetraacetic acid tetrasodium salt, and the weight ratio of the ferrous sulfate, the sodium formaldehyde sulfoxylate and the ethylenediaminetetraacetic acid tetrasodium salt is 1 (3-5) to 2.5.
Preferably, the molecular weight regulator is tertiary dodecyl mercaptan and/or n-dodecyl mercaptan. The molecular weight regulator is selected from the above types, so that the molecular weight of the styrene-butadiene rubber can be more effectively regulated, and simultaneously, the weight content of styrene units in the modified styrene-butadiene rubber and the Mooney viscosity of the modified styrene-butadiene rubber in the polymerization reaction process can be more effectively controlled to be kept in a more proper range, thereby further improving the cutting resistance of the modified styrene-butadiene rubber. Preferably, the electrolyte comprises one or more of phosphoric acid, potassium hydroxide, ethylenediaminetetraacetic acid tetrasodium salt, and sodium m-methine-dinaphthalenesulfonate. The electrolyte is selected from the above types, and can be used together with a molecular weight regulator to control the viscosity of the reaction system and simultaneously facilitate the improvement of the conversion rate of polymerization. More preferably, the electrolyte comprises phosphoric acid, potassium hydroxide, ethylene diamine tetraacetic acid tetrasodium salt and sodium m-methine dinaphthalene sulfonate, and the weight ratio of the four is (20-30): (30-50): 3: (10-20).
Preferably, the raw material liquid further comprises 0.07-0.15 parts by weight of a molecular weight regulator and 0.63-1.03 parts by weight of an electrolyte. Thus, the molecular weight regulator has better control effect on the weight content of styrene units in the modified styrene-butadiene rubber and the Mooney viscosity in the polymerization reaction process. Meanwhile, the molecular weight regulator and the electrolyte have better synergistic effect, and the effect of controlling the viscosity of a reaction system is better.
Preferably, the terminating agent is isopropylhydroxylamine and/or a sulfate. The terminator is selected from the above-mentioned species and can terminate the polymerization reaction in a smaller amount. In a preferred embodiment, the amount of the terminating agent is 0.055% to 0.150% by weight of the emulsifier. The sulfate may be selected from sodium persulfate and the like which are conventional in the art, and which may be selected by one skilled in the art, and will not be described herein in detail.
The invention also provides modified styrene-butadiene rubber prepared by the preparation method.
Based on the above reasons, the modified styrene-butadiene rubber of the present invention has better weight content of styrene units, better mooney viscosity of the modified styrene-butadiene rubber, and the weight content of styrene units in the modified styrene-butadiene rubber is 38% to 42%; the Mooney viscosity of the modified styrene-butadiene rubber is 55-65. The better weight content of the styrene unit and the Mooney viscosity promote the better cutting resistance of the modified styrene-butadiene rubber.
The invention also provides application of the modified styrene-butadiene rubber as a manufacturing material of an engineering tire.
Based on the reasons, compared with the traditional styrene butadiene rubber, the cutting resistance of the modified styrene butadiene rubber is improved by more than 25 percent, and the modified styrene butadiene rubber is an ideal rubber for engineering tires.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
And (2) carrying out vacuum and nitrogen replacement on a polymerization kettle, sequentially adding 42 parts of first part of styrene, 54 parts of butadiene, 4.5 parts of emulsifier disproportionated potassium abietate soap, 0.63 part of electrolyte, 0.065 part of reducing agent, 0.10 part of tert-dodecyl mercaptan and 190 parts of water into the polymerization kettle in parts by weight, adding 0.065 part of initiator hydrogen peroxide p-menthane when the temperature of the polymerization kettle is reduced to 5 ℃, carrying out polymerization reaction, adding a second part of styrene (the weight ratio of the second part of styrene to the first part of styrene is 1:3) when the conversion rate reaches 10%, and continuing the reaction, adding a terminator isopropyl hydroxylamine (the amount is 0.11% of the weight of the emulsifier) to terminate the reaction when the conversion rate reaches 60%, thereby obtaining a polymerization glue solution. And adding the polymerized glue solution into a dilute sulfuric acid solution with the concentration of 0.5%, stirring, controlling the temperature to be 60 ℃ for condensation, and then washing and drying to obtain the modified styrene-butadiene rubber.
Wherein the electrolyte comprises phosphoric acid, potassium hydroxide, ethylene diamine tetraacetic acid tetrasodium salt and sodium m-methine dinaphthalene sulfonate, and the weight ratio of the four is 20; the reducing agent comprises ferrous sulfate, sodium formaldehyde sulfoxylate and ethylenediaminetetraacetic acid tetrasodium salt, and the weight ratio of the ferrous sulfate to the sodium formaldehyde sulfoxylate to the ethylenediaminetetraacetic acid tetrasodium salt is 1.
Example 2
The polymerization kettle is subjected to vacuum and nitrogen replacement, 43 parts of first part of styrene, 52 parts of butadiene, 4.65 parts of emulsifier disproportionated rosin potassium soap, 1.03 parts of electrolyte, 0.065 part of reducing agent, 0.10 part of tert-dodecyl mercaptan and 190 parts of water are sequentially added into the polymerization kettle in parts by weight, when the temperature of the polymerization kettle is reduced to 5 ℃, 0.065 part of initiator hydrogen peroxide is added to the menthane for polymerization, when the conversion rate reaches 11%, a second part of styrene (the weight ratio of the second part of styrene to the first part of styrene is 1:5) is added for continuous reaction, and when the reaction conversion rate reaches 60%, a terminator isopropyl hydroxylamine (the using amount is 0.129% of the weight of the emulsifier) is added for terminating the reaction to obtain a polymerization glue solution. And adding the polymerized glue solution into a dilute sulfuric acid solution with the concentration of 0.5%, stirring, controlling the temperature to be 60 ℃ for condensation, and then washing and drying to obtain the modified styrene-butadiene rubber.
Wherein the electrolyte comprises phosphoric acid, potassium hydroxide, ethylene diamine tetraacetic acid tetrasodium salt and sodium m-methine dinaphthalene sulfonate, and the weight ratio of the four is 30; the reducing agent comprises ferrous sulfate, sodium formaldehyde sulfoxylate and ethylenediaminetetraacetic acid tetrasodium salt, and the weight ratio of the ferrous sulfate to the sodium formaldehyde sulfoxylate to the ethylenediaminetetraacetic acid tetrasodium salt is 1.
Example 3
The polymerization kettle is subjected to vacuum and nitrogen replacement, according to parts by weight, 45 parts of first part of styrene, 50 parts of butadiene, 4.55 parts of emulsifier disproportionated rosin potassium soap, 0.83 part of electrolyte, 0.065 part of reducing agent, 0.10 part of tert-dodecyl mercaptan and 190 parts of water are sequentially added into the polymerization kettle, when the temperature of the polymerization kettle is reduced to 5 ℃, 0.065 part of initiator hydrogen peroxide is added to the menthane for polymerization, when the conversion rate reaches 12%, a second part of styrene (the weight ratio of the second part of styrene to the first part of styrene is 1:6) is added for continuous reaction, and when the reaction conversion rate reaches 60%, a terminator isopropyl hydroxylamine (the amount is 0.110% of the weight of the emulsifier) is added for terminating the reaction to obtain a polymerization glue solution. And adding the polymerized glue solution into a dilute sulfuric acid solution with the concentration of 0.5%, stirring, controlling the temperature to be 60 ℃ for condensation, and then washing and drying to obtain the modified styrene-butadiene rubber.
Wherein the electrolyte comprises phosphoric acid, potassium hydroxide, ethylene diamine tetraacetic acid tetrasodium salt and sodium m-methine dinaphthalene sulfonate, and the weight ratio of the four is 25; the reducing agent comprises ferrous sulfate, sodium formaldehyde sulfoxylate and ethylenediaminetetraacetic acid tetrasodium salt, and the weight ratio of the ferrous sulfate to the sodium formaldehyde sulfoxylate to the ethylenediaminetetraacetic acid tetrasodium salt is 1.
Example 4
The only difference from example 1 is that the first styrene part is 40 parts by weight.
Example 5
The only difference from example 1 is that the first styrene part by weight was 47 parts.
Example 6
The only difference from example 1 is the amount of styrene used in the second portion. The weight ratio of the second portion of styrene to the first portion of styrene is 1:8.
Comparative example 1
Performing vacuum and nitrogen replacement on a polymerization kettle, sequentially adding 35 parts by weight of first part of styrene, 40 parts by weight of butadiene, 3.55 parts by weight of emulsifier disproportionated rosin potassium soap, 0.83 part by weight of electrolyte, 0.055 part by weight of reducing agent, 0.04 part by weight of tert-dodecyl mercaptan and 190 parts by weight of water into the polymerization kettle, adding 0.045 part by weight of initiator hydrogen peroxide to menthane when the temperature of the polymerization kettle is reduced to 5 ℃, performing polymerization reaction, adding a second part of styrene (the weight ratio of the second part of styrene to the first part of styrene is 1:6) when the conversion rate reaches 30%, continuing to react, and adding a terminator isopropyl hydroxylamine (the amount is 0.141% of the weight of the emulsifier) when the reaction conversion rate reaches 60% to terminate the reaction to obtain a polymerization glue solution. And adding the polymerized glue solution into a dilute sulfuric acid solution with the concentration of 0.5%, stirring, controlling the temperature to be 60 ℃ for condensation, and then washing and drying to obtain a styrene butadiene rubber sample.
Wherein the electrolyte comprises phosphoric acid, potassium hydroxide, ethylene diamine tetraacetic acid tetrasodium salt and sodium m-methine dinaphthalene sulfonate, and the weight ratio of the four is 25; the reducing agent comprises ferrous sulfate, sodium formaldehyde sulfoxylate and ethylenediaminetetraacetic acid tetrasodium salt, and the weight ratio of the ferrous sulfate to the sodium formaldehyde sulfoxylate to the ethylenediaminetetraacetic acid tetrasodium salt is 1.
Comparative example 2
Carrying out vacuum and nitrogen replacement on a polymerization kettle, directly adding 46 parts of styrene, 54 parts of butadiene, 4.5 parts of emulsifier disproportionated potassium rosinate soap, 0.63 part of electrolyte, 0.065 part of reducing agent, 0.10 part of tert-dodecyl mercaptan and 190 parts of water into the polymerization kettle according to parts by weight, adding 0.065 part of initiator hydrogen peroxide p-menthane when the temperature of the polymerization kettle is reduced to 5 ℃, carrying out a polymerization experiment, and adding a terminator isopropyl hydroxylamine (the amount is 0.111% of the weight of the emulsifier) to terminate the reaction when the conversion rate reaches 60% to obtain a polymerization glue solution. And adding the polymerized glue solution into a dilute sulfuric acid solution with the concentration of 0.5%, stirring, controlling the temperature at 60 ℃, condensing, washing and drying to obtain a styrene-butadiene rubber sample.
Wherein the electrolyte comprises phosphoric acid, potassium hydroxide, ethylene diamine tetraacetic acid tetrasodium salt and sodium m-methine dinaphthalene sulfonate, and the weight ratio of the four is 25; the reducing agent comprises ferrous sulfate, sodium formaldehyde sulfoxylate and ethylenediaminetetraacetic acid tetrasodium salt, and the weight ratio of the ferrous sulfate to the sodium formaldehyde sulfoxylate to the ethylenediaminetetraacetic acid tetrasodium salt is 1.
Comparative example 3
Conventional styrene butadiene rubber SBR1500E.
And (3) performance testing:
the preparation of the rubber compound and vulcanized rubber and the performance test are carried out according to GB 8655-2006.
The styrene butadiene rubber cutting test is a test of the cutting resistance of vulcanized styrene butadiene rubber and elastic materials. The instrument model is a high-speed rail company GT-7012-Q rubber dynamic cut-resistant testing machine, a cutter cuts a sample under a certain inclination angle and a certain load, and the cut volume or the cut index of the sample within a certain mileage is measured. The cutting resistance of each styrene-butadiene rubber is represented by detecting the weight loss of each styrene-butadiene rubber after the cutting test in the examples and the comparative examples, and the smaller the weight loss percentage of the styrene-butadiene rubber is, the better the cutting resistance is. The test results are shown in table 1 below:
TABLE 1
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. A preparation method of modified styrene-butadiene rubber is characterized by comprising the following steps:
s1, preparing a raw material liquid comprising a first part of styrene, butadiene, an emulsifier, a reducing agent and water, and adding an initiator into the raw material liquid to perform emulsion polymerization; wherein the raw material liquid comprises 40-47 parts by weight of the first part of styrene, 48-56 parts by weight of the butadiene, 4.0-5.5 parts by weight of the emulsifier, 0.065-0.085 part by weight of the reducing agent and 180-200 parts by weight of the water, and the weight part of the initiator is 0.06-0.12 part by weight;
and S2, adding a second part of styrene into the emulsion polymerization reaction system and continuing to react when the reaction conversion rate reaches 10-12%, and stopping the reaction when the reaction conversion rate reaches 60%, thereby obtaining the modified styrene-butadiene rubber.
2. The method for preparing modified styrene-butadiene rubber according to claim 1, wherein the weight ratio of the second part of styrene to the first part of styrene is 1 (3-6).
3. The method for preparing modified styrene-butadiene rubber according to claim 1 or 2, wherein the raw material liquid comprises, by weight, 42 to 45 parts of the styrene, 50 to 54 parts of the butadiene, 4.5 to 5.0 parts of the emulsifier, 0.065 to 0.085 part of the reducing agent, and 180 to 200 parts of water, and the initiator is 0.06 to 0.12 part by weight.
4. The process for producing modified styrene-butadiene rubber according to any one of claims 1 to 3, wherein the raw material liquid further comprises 0.07 to 0.15 parts by weight of a molecular weight modifier and 0.63 to 1.03 parts by weight of an electrolyte.
5. The process for producing modified styrene-butadiene rubber according to any one of claims 1 to 4,
the step S1 includes: carrying out vacuum and nitrogen replacement on a polymerization kettle, adding raw materials into the polymerization kettle to form a raw material liquid, reducing the temperature in the polymerization kettle to be below 5 ℃, and then adding the initiator into the raw material liquid to carry out the emulsion polymerization reaction;
the step S2 includes: adding a terminator into the polymerization kettle to terminate the reaction when the reaction conversion rate reaches 60% to obtain a polymerization glue solution; and adding the polymerized glue solution into a dilute sulfuric acid solution for coagulation, washing and drying to obtain the modified styrene-butadiene rubber.
6. The method of producing modified styrene-butadiene rubber according to any one of claims 1 to 5, wherein the emulsifier is a disproportionated potassium rosinate soap and/or a fatty acid sodium soap;
preferably, the initiator is p-menthane hydroperoxide and/or diisopropylbenzene hydroperoxide;
preferably, the reducing agent comprises one or more of ferrous sulfate, sodium formaldehyde sulfoxylate and ethylenediaminetetraacetic acid tetrasodium salt; preferably, the reducing agent comprises ferrous sulfate, sodium formaldehyde sulfoxylate and ethylenediaminetetraacetic acid tetrasodium salt, and the weight ratio of the ferrous sulfate, the sodium formaldehyde sulfoxylate and the ethylenediaminetetraacetic acid tetrasodium salt is 1 (3-5) to 2.5.
7. The process for producing modified styrene-butadiene rubber according to claim 4, wherein the molecular weight modifier is t-dodecyl mercaptan and/or n-dodecyl mercaptan;
preferably, the electrolyte comprises one or more of phosphoric acid, potassium hydroxide, ethylenediaminetetraacetic acid tetrasodium salt, and sodium m-methine-dinaphthalenesulfonate; preferably, the electrolyte comprises phosphoric acid, potassium hydroxide, ethylene diamine tetraacetic acid tetrasodium salt and sodium m-methine dinaphthalene sulfonate, and the weight ratio of the four is (20-30): (30-50): 3: (10-20).
8. The method for producing modified styrene-butadiene rubber according to claim 5, wherein the terminator is isopropyl hydroxylamine and/or sulfate; preferably, the amount of the terminating agent is 0.055-0.150% of the weight of the emulsifier.
9. A modified styrene-butadiene rubber, characterized in that it is produced by the production method according to any one of claims 1 to 8.
10. The modified styrene-butadiene rubber according to claim 9, wherein the weight content of styrene units in the modified styrene-butadiene rubber is 38 to 42%; the Mooney viscosity of the modified styrene-butadiene rubber is 55-65.
11. The modified styrene-butadiene rubber prepared by the preparation method of any one of 1 to 8 is applied as a material for manufacturing engineering tires.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5583173A (en) * | 1995-04-10 | 1996-12-10 | The Goodyear Tire & Rubber Company | Process for preparing styrene-butadiene rubber |
| US6393655B1 (en) * | 1998-02-23 | 2002-05-28 | The Goodyear Tire & Rubber Company | Rubber products having better abrasion resistance |
| CN103450396A (en) * | 2012-06-01 | 2013-12-18 | 中国石油天然气股份有限公司 | Emulsion polymerization method for preparing tractable butadiene styrene rubber |
| CN109776726A (en) * | 2017-11-15 | 2019-05-21 | 中国石油天然气股份有限公司 | The preparation method and butadiene-styrene rubber of butadiene-styrene rubber |
-
2021
- 2021-05-12 CN CN202110519146.7A patent/CN115340632A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5583173A (en) * | 1995-04-10 | 1996-12-10 | The Goodyear Tire & Rubber Company | Process for preparing styrene-butadiene rubber |
| US6393655B1 (en) * | 1998-02-23 | 2002-05-28 | The Goodyear Tire & Rubber Company | Rubber products having better abrasion resistance |
| CN103450396A (en) * | 2012-06-01 | 2013-12-18 | 中国石油天然气股份有限公司 | Emulsion polymerization method for preparing tractable butadiene styrene rubber |
| CN109776726A (en) * | 2017-11-15 | 2019-05-21 | 中国石油天然气股份有限公司 | The preparation method and butadiene-styrene rubber of butadiene-styrene rubber |
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