CN111777729A - Wide-distribution, high-elasticity and functionalized solution-polymerized styrene-butadiene rubber, preparation method thereof and application thereof in tire tread rubber - Google Patents
Wide-distribution, high-elasticity and functionalized solution-polymerized styrene-butadiene rubber, preparation method thereof and application thereof in tire tread rubber Download PDFInfo
- Publication number
- CN111777729A CN111777729A CN201910263732.2A CN201910263732A CN111777729A CN 111777729 A CN111777729 A CN 111777729A CN 201910263732 A CN201910263732 A CN 201910263732A CN 111777729 A CN111777729 A CN 111777729A
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- Prior art keywords
- butadiene rubber
- polymerized styrene
- solution
- distribution
- rubber
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- 238000009826 distribution Methods 0.000 title claims abstract description 65
- 229920001971 elastomer Polymers 0.000 title claims abstract description 62
- 239000005060 rubber Substances 0.000 title claims abstract description 56
- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 82
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 20
- -1 alkyl lithium Chemical compound 0.000 claims abstract description 19
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims abstract description 18
- 150000001993 dienes Chemical class 0.000 claims abstract description 15
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims abstract description 14
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 12
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 9
- 230000001112 coagulating effect Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 49
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 39
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical group [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 29
- 239000006229 carbon black Substances 0.000 claims description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 238000007306 functionalization reaction Methods 0.000 claims description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003921 oil Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- 239000005062 Polybutadiene Substances 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
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- 230000000694 effects Effects 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- MAOBFOXLCJIFLV-UHFFFAOYSA-N (2-aminophenyl)-phenylmethanone Chemical compound NC1=CC=CC=C1C(=O)C1=CC=CC=C1 MAOBFOXLCJIFLV-UHFFFAOYSA-N 0.000 claims description 3
- 230000003712 anti-aging effect Effects 0.000 claims description 3
- YNOGYQAEJGADFJ-UHFFFAOYSA-N oxolan-2-ylmethanamine Chemical compound NCC1CCCO1 YNOGYQAEJGADFJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
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- 239000003292 glue Substances 0.000 description 25
- 230000008569 process Effects 0.000 description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
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- 238000007599 discharging Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
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- 239000000155 melt Substances 0.000 description 5
- 239000012190 activator Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012954 diazonium Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 3
- 238000011925 1,2-addition Methods 0.000 description 2
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000008049 diazo compounds Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 239000005051 trimethylchlorosilane Substances 0.000 description 2
- JJUIQZSNOOQTTK-UHFFFAOYSA-N (6-methylidenecyclohexa-2,4-dien-1-yl)-phenylmethanone Chemical class C=C1C(C(=O)C2=CC=CC=C2)C=CC=C1 JJUIQZSNOOQTTK-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 1
- XXWQHWRBCTWNOL-UHFFFAOYSA-N 3-[ethoxy-methyl-(2-trimethylsilylethoxy)silyl]propan-1-amine Chemical compound C[Si](C)(C)CCO[Si](OCC)(C)CCCN XXWQHWRBCTWNOL-UHFFFAOYSA-N 0.000 description 1
- SLSKAIZCBJQHFI-UHFFFAOYSA-N 3-triethoxysilyl-n,n-bis(trimethylsilyl)propan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCN([Si](C)(C)C)[Si](C)(C)C SLSKAIZCBJQHFI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- QOHGRBMFOXKPAJ-UHFFFAOYSA-M FC(F)(F)[Sn]Cl Chemical compound FC(F)(F)[Sn]Cl QOHGRBMFOXKPAJ-UHFFFAOYSA-M 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
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- 239000003242 anti bacterial agent Substances 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 1
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- HASGOCLZFTZSTN-UHFFFAOYSA-N cyclohexane;hexane Chemical compound CCCCCC.C1CCCCC1 HASGOCLZFTZSTN-UHFFFAOYSA-N 0.000 description 1
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- CKVWBMJEETWJTF-UHFFFAOYSA-N lithium;tributyltin Chemical compound CCCC[Sn]([Li])(CCCC)CCCC CKVWBMJEETWJTF-UHFFFAOYSA-N 0.000 description 1
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- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 239000011115 styrene butadiene Substances 0.000 description 1
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- 239000011135 tin Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
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- 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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/046—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- 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
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- C08K3/22—Oxides; Hydroxides of metals
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- 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
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a wide-distribution, high-elasticity and functionalized solution-polymerized styrene-butadiene rubber, a preparation method thereof and application thereof in tire tread rubber, wherein the preparation method comprises the following steps: adding divinyl benzene, conjugated diene and alkyl lithium initiator into an anionic polymerization solution system to carry out polymerization reaction; sequentially adding a diazo reagent and a styrene/butadiene mixed monomer to perform random copolymerization reaction; and finally, adding a polar end-capping reagent for end-capping reaction, hydrolyzing and coagulating to obtain the solution-polymerized SSBR with wide molecular weight mass distribution (D is not less than 1.8), long and short branched chains, wide molecular fractions and high melt elasticity, wherein functional groups at the tail ends of molecular chains are closed end to end, the end-capping rate is more than 75%, and the rubber can obviously improve the processing performance and reduce the rolling resistance of the tire by replacing the conventional SSBR used for the tire tread rubber.
Description
Technical Field
The invention relates to an elastomer material, in particular to a wide-distribution, high-elasticity and functionalized solution-polymerized styrene-butadiene rubber, and also relates to an application of the solution-polymerized styrene-butadiene rubber in a tire tread rubber, belonging to the field of preparation of elastic materials of tire tread rubbers.
Background
As the solution polymerized styrene butadiene rubber (SSBR) adopts an anion polymerization method, the product structure is easy to adjust, and the brand is rich. Compared with Emulsion Styrene Butadiene Rubber (ESBR), SSBR can reduce the rolling resistance of the tire by 20-30% and improve the wet skid resistance by 30-40%. The SSBR is used as a main material of a tire, and is developed to have intelligentized processing and high performance of safety, comfort and energy saving during running of the tire. Functionalization is the most efficient method to achieve high performance of SSBR. That is, the trend of SSBR is to control the content of vinyl unit in the molecule at 57-75%, the molecular weight distribution index D is greater than 1.90, the molecular chain of the polymer has long chain branching, high entanglement, high melt elasticity, low cold flow, and the blocking rate of functional group or molecular terminal polarity in the molecular chain is 75-100%.
In the aspect of processability, the ESBR is continuous emulsion polymerization, the molecular weight distribution index of the polymer presents trailing monomodal wide distribution, the molecular weight distribution index D can reach more than 3.0, and the molecular distribution is extremely wide; the melt elasticity of the polymer raw rubber is the greatest in synthetic rubbers, so the processability is inferior to that of natural rubber only. However, compared with the existing SSBR prepared by conventional batch polymerization and continuous method, the existing SSBR prepared by conventional batch polymerization is far inferior to the ESBR in terms of processing units of tires, such as mixing, extrusion, calendering, sheeting, tread application, green tire molding, and the like, and especially the processing behavior of the composite component of the "silicon formula" filled with white carbon black is deficient. Soltman is explicitly mentioned in the book "stereorubbers": the reason for the poor processability of SSBR is that the molecular weight distribution of SSBR is too narrow, the molecular weight is too low, and the melt elasticity is too low. The molecular chain is subjected to long-chain and short-chain branching in a chain growth stage in the SSBR synthesis, so that the weight average Molecular Weight (MW) of the polymer is improved, the molecular weight distribution of the polymer is widened, the melt elasticity of the polymer is improved, and the processability of the polymer can be improved. But the fabrication processes and conditions are not specifically described herein. The molecular weight distribution index of SSBR prepared by the existing commercial continuous polymerization method, such as VSL-5025, SSBR2560, SSBR2557S, T3830 and T3835, is less than 1.80, while the D of SSBR2563, HPR-850, Y-031, F-1204 and the like polymerized by a discontinuous method is less than or equal to 1.5. Such rubbers have been more difficult to meet with the development of "all white carbon black filled formulations" for producing tires of lower rolling resistance grades. For example, U.S. Pat. No. 4,4451576 (1984), U.S. Pat. No. 4,4424323 (1984), Fireston/Lohr. D.F. Moldifier with light distribution and microtreter modifier for elastomers, describe the addition of a suitable amount of a dinitrogen compound to the polymerization of butadiene-styrene, for example, to increase the molecular weight distribution index of the polymer to 2.0 to 5.0 under the action of a regulator of dinitrogen reagent/active lithium ═ (1 to 2)/1 (molar ratio). However, the molecular fraction of the crude rubber polymer is larger and shows good melt rheological property, but the molecular chain of the crude rubber polymer is linear molecule, so that the crude rubber polymer shows lower melt elasticity and low relative density and entanglement degree; in addition, the content of vinyl units in the molecules of the polymer is not less than 45.0 percent, the polymer can only be filled with general carbon black to prepare rubber products, the comprehensive index of the polymer is not suitable for being used as an intelligent banburying process, and the requirement of high-performance tire materials can not be met, meanwhile, the dosage range of the diazo reagent in the polymerization reaction in the existing patent is wider, namely 0.2-2.0 m mol/100g of polymer, the copolymerization conversion rate of styrene-butadiene is 80.4 percent, and the synthesis preparation of SSBR is of no practical significance.
In addition, the research on the processing behavior of SSBR2557S in the text "application of domestic solution-polymerized styrene-butadiene rubber in green tire tread rubber" 2016(6) in tire industry "by Qingyun et al" shows that: compared with related SBR, the surface state is poorer and the rubber discharge is looser in the mixing process of the rubber material in the SSBR large-matching test; the surface state of the rubber extruded tread is relatively rough, the extruded part is thin, the mouth shape expansion is small, the joint viscosity of the extruded tread is poor when the extruded tread is used in a forming procedure, and the phenomenon of head warping still occurs after compression by a compression roller. These are related to the relatively narrow molecular mass distribution of the SSBR size. Also in Zhang Jian et al "Performance Studies in the tire industry 2016(6) oil extended solution-polymerized styrene butadiene rubber in high Performance tire tread rubber" a study of a linear SSBR2563 exhibiting a bimodal narrow molecular weight distribution for intermittent polymerization showed that: the prepared rubber compound has low strength and poor self-adhesion and caking property, and the white carbon black is not uniformly dispersed in the rubber compound; the roller sticking and the film bottom roller are difficult to occur in the rubber compound in the high oil-filled formula.
For the functionalization of SSBR, such documents as JP 2009287020A describe rubbers obtained by polymerizing butadiene and styrene in cyclohexane in the presence of bistetrahydrofurfurylpropane and butyllithium, modified with 3-N, N-bis (trimethylsilyl) aminopropyl (methyl) diethoxysilane, which is of the coupled type, the polar nitrogen atom also being in the middle stage of the polymer. David f, lawson, Uniontown et al US5616704A solid nitrile polymerization initiators describe the synthesis of SSBR by reacting secondary amine compounds with butyl lithium to form secondary amino lithium as the initiator for the polymerization of styrene and butadiene and finally terminating the polymerization with trialkyltin chloride or 4,4 ' -bis (methylene) benzophenones or other N, N ' -dialkyl-amino-alkyl ketones or aldehydes or N, N ' -dialkyl-amino-alkyl alkenes. However, the secondary amino lithium is affected by temperature and equilibrium reaction in the preparation process, and a small amount of secondary amine always exists in the secondary amino lithium solution, which seriously affects the polymerization reaction kinetics, causes incomplete polymerization reaction, does not remove the molecular weight of the polymer, and the like. Hergenrother, William L, EP0493839B1, "Tin crosslinking activators and products with reduced hysteresis properties". In this document, lithium tributyltin is used to initiate polymerization, and finally, the polymer is terminated with tributyltin chloride. Carlo kanz, Mamer (LU) US2012/0123018A1 describes polymers of butyl lithium initiated butadiene-styrene coupled with amine-containing silicon, such coupling agents are N, N-bis-trimethylsilyl-aminopropyl-triethoxysilane, N-bis-trimethylsilyl-aminoethylene-triethoxysilane, N-bis-trimethylsilyl-aminopropyl-methyldimethoxysilane, N-bis-trimethylsilyl-aminopropyl-methyldimethoxysilane and the like, high performance tread rubber formulations are described which contain aminosiloxane coupled SSBR in addition to high cis-BR, white carbon black, tackifying resins and the like, but the aminosiloxane coupled SSBR has an end-capping ratio of less than 50% and the prepared polymers have molecular weight distribution indices of less than 1.6, the melt elasticity is small, and the processability of the rubber in the formula of the white carbon black is poor.
To date, the discontinuous process for preparing a wide molecular weight distribution, high melt elasticity, functionalized solution-polymerized styrene-butadiene rubber has not been completely reported in the literature.
Disclosure of Invention
Aiming at the defects of the conventional tire tread rubber SSBR elastomer material, the invention aims to provide the SSBR with wide molecular weight mass distribution (D is not less than 1.8), long and short branched chains, wide molecular fractions and high melt elasticity, wherein functional groups at the tail ends of molecular chains are closed end to end, the end capping rate is more than 75%, and the rubber can obviously improve the processing performance and reduce the rolling resistance of a tire by replacing the conventional SSBR for the tire tread rubber.
The second purpose of the invention is to provide a method for preparing the solution polymerized butadiene styrene rubber with wide distribution, high elasticity and functionalization, which has simple operation, low cost and mild condition.
The third purpose of the invention is to provide the application of the wide-distribution, high-elasticity and functionalized solution-polymerized styrene-butadiene rubber, the solution-polymerized styrene-butadiene rubber has higher vinyl unit content, intelligent mixing and easy processing, and the manufactured tire has the advantages of low rolling resistance, good wet skid resistance and the like. The solution-polymerized styrene-butadiene rubber has the advantages that the tail end functional groups of the molecular chain of the solution-polymerized styrene-butadiene rubber are closed end to end, the end-blocking rate is more than 75%, the tread rubber has lower rolling resistance, the solution-polymerized styrene-butadiene rubber has wide molecular weight and mass distribution (D is not less than 1.8), and meanwhile, the solution-polymerized styrene-butadiene rubber has long and short branched chains, wide molecular weight and high melt elasticity, and can improve the processing performance of the polymer used as the tread rubber in a formula of completely filling white carbon black.
In order to achieve the above technical objects, the present invention provides a method for preparing a solution-polymerized styrene-butadiene rubber having wide distribution, high elasticity and functionalization, comprising the steps of:
1) adding divinyl benzene, conjugated diene and alkyl lithium initiator into the anionic polymerization solution system to carry out polymerization reaction;
2) sequentially adding a diazo reagent and a styrene/butadiene mixed monomer into an anionic polymerization solution system to perform random copolymerization reaction;
3) adding a polar end capping agent into an anionic polymerization solution system for end capping reaction, and then hydrolyzing and coagulating to obtain the product.
In a preferred embodiment, the anionic polymerization solution system comprises at least one activity regulator selected from tetrahydrofuran, tetrahydrofurfuryl alcohol ethyl ether, ditetrahydrofurfuryl propane, tetrahydrofurfuryl amine, tetrahydrofurfuryl alcohol hexyl ether. The activity regulator is mainly used for regulating the content of 1, 2-addition units of butadiene, and at least one of tetrahydrofuran, tetrahydrofurfuryl alcohol ethyl ether, ditetrahydrofurfuryl propane, tetrahydrofurfuryl amine, tetrahydrofurfuryl alcohol hexyl ether and the like which are commonly used for anionic polymerization can be selected as an activator.
In a preferable scheme, the concentration of the activity regulator in an anionic polymerization solution system is 250-450 mg/L. The vinyl content of a polybutadiene section in the synthesized SSBR crude rubber is 50-70%.
In a preferred scheme, the molar ratio of the divinyl benzene to the alkyl lithium initiator is 1 (2-3). The excess alkyllithium is primarily to make up for the alkyllithium lost by reaction with moisture in the solvent.
In a preferable scheme, the dosage of the conjugated diene relative to the alkyl lithium initiator is 200-500 g/mol.
In a preferred embodiment, the divinylbenzene is a mixture comprising ortho, meta and para isomers.
In a preferred embodiment, the conjugated diene includes butadiene and/or isoprene.
In a preferred embodiment, the alkyl lithium initiator is butyl lithium.
In a preferred embodiment, the diazo reagent comprises 1, 5-diazobicyclo [4,3,0] -non-5-ene and/or 1, 8-diazobicyclo [5,4,0] -non-5-ene. The diazo reagent used in the present invention is a regulator of molecular mass distribution index, and is preferably at least one of commercially available diazo compounds containing no active hydrogen atom, such as 1, 5-diazobicyclo [4,3,0] -non-5-ene (DBN) and 1, 8-diazobicyclo [5,4,0] -non-5-ene (DBU). It is worth further describing that such compounds are widely used as intermediates for antibiotics, basic catalysts for chemical reactions, accelerators, hardeners for epoxy resins, etc., and are low-toxic and odorless.
The inventor researches to show that the diazo reagent is caused by lithium (-CH) from an active chain on a nitrogen atom of the diazo reagent in SSBR polymerization2Li+) The electron on the molecular chain of the active polymer generates 1,2 of proton from the electron on the molecular chain of the active polymer when the electron is converted from the previous electrophilicity to the nucleophilicityMigration, which is a process involving competition, relatively passive proton migration, and delayed history, and the competition between proton 1, 2-migration and electrophilic capture causes the speed of molecular chain growth of living polymer to be different, i.e. the chain growth of polymer is random and irregular. Namely, the diazo compound participates in the polymerization reaction of butadiene-styrene active lithium, which is an asymmetric catalytic multicomponent reaction, and finally the obtained polymer is in the distribution of multi-component molecular chain length and molecular mass of continuous segments with different lengths, namely the molecular weight distribution index of the polymer is widened.
In a preferred embodiment, the molar ratio of the diazonium reagent to the alkyl lithium is 1 (1.4-2.0). The research shows that: in the polymerization reaction, when the dosage of the diazo reagent is too high, the polymerization reaction speed is extremely slow or no reaction is carried out; when the dosage of the diazo reagent is too low, the polymerization reaction speed is higher or equal to that the polymerization system does not contain the diazo reagent, and finally the molecular mass distribution index D of the polymer is less than 1.3. The most preferred ratio of diazonium reagent (DBU or DBN) to butyllithium added during polymerization in SSBR synthesis is therefore: diazo reagent/NBL (molar ratio) is 1/(1.4-2.0); or the addition amount of the mixed monomer is 0.8-1.2 mmol/100g of the monomer.
Preferably, the mass ratio of styrene to butadiene in the styrene/butadiene mixed monomer is (20-40)/(80-60).
Preferably, the polar end-capping agent comprises at least one of chlorotrimethyltin, chlorotrimethylsilicon, aminobenzophenones, N' -dimethylimidazolidinone, and organic acid esters. The polar end-capping agent of the present invention may preferably be a mono-active functional group containing an organic compound composed of atoms of tin, oxygen, nitrogen, sulfur, silicon, etc., such as at least one of chlorotrifluoromethyltin, chlorotrimethylsilicon, aminobenzophenones, N' -dimethylimidazolidinone, organic acid esters, etc., and the molar amount of the end-capping agent is 0.7 to 1.0 times the amount of the butyl lithium initiator added. The addition method is that the cyclohexane solution is prepared, the cyclohexane solution is added after the monomer reaction is finished, and the end capping is reacted for 20-25 min at 55-80 ℃ to obtain the F-SSBR. According to the conformational analysis of macromolecular chains, the hysteresis loss of the tread rubber is mainly caused by the fact that the chain links with larger freedom degree between the final crosslinking points and the chain ends of the network macromolecules are difficult to participate in the effective elastic recovery process of the macromolecules, and therefore, the energy lost in the periodic deformation is easy to be converted into heat. When the chain ends are introduced with functional groups which "passivate" the free chain ends and which in turn enhance the affinity of the filler (e.g. white carbon black), the hysteresis loss of the tread rubber is improved, i.e. the rolling resistance of the tire is reduced.
In a preferred embodiment, the molar ratio of the polar capping agent to the alkyllithium is (0.7 to 1.0): 1.
In the preferable scheme, the temperature of the polymerization reaction is 50-60 ℃, the pressure is 0.3-0.5 MPa, and the time is 15-20 min.
In the preferable scheme, the initial temperature of the copolymerization reaction is 50-58 ℃, the pressure is 0.3-0.5 MPa, the highest temperature is less than 75 ℃, the temperature rise rate is controlled within the range of 1.0-1.3 ℃/min, the temperature rise time is 12-20 min, and the copolymerization reaction is carried out for 40-50 min under the adiabatic condition when the temperature reaches the highest temperature.
In the preferable scheme, the temperature of the end-capping reaction is 50-75 ℃, the pressure is 0.3-0.5 MPa, and the time is 20-25 min.
In the polymerization process of the present invention, the preferred feeding manner is: DVB and a small amount of compatibilized conjugated diene monomer are added into a polymerization kettle with a quantitative solvent at one time, then butyl lithium is added, and the reaction is initiated for 15-20 min at the temperature of 50-60 ℃ to form the active species of divinyl dilithium with the formula 1.
Li+-R-CH2CH(B)-C6H4-(B)CHCH2-(R)-Li+
Formula 1
wherein-C6H4-is a benzene ring, B is a butyl group, R is a conjugated diene oligomeric unit.
The aim of adding a certain amount of conjugated diene monomer in the preparation process of the active species is to introduce the conjugated diene monomer into a molecule of the formula 1, increase the solubility of dilithium or multi-lithium oligomeric diene active lithium in a polymerization solvent, and facilitate the subsequent homogeneous polymerization of mixed monomers, wherein the preferred conjugated diene is butadiene or isoprene, and the dosage of the conjugated diene is 200-500 g/mol of active lithium.
In the preparation process of the solution polymerized styrene butadiene rubber, cyclohexane and/or hexane are/is used as a solvent, and the concentration of a polymerized monomer in the solvent is 10-15 wt%.
The invention also provides a wide-distribution, high-elasticity and functionalized solution-polymerized styrene-butadiene rubber which is obtained by the preparation method.
Preferably, the molecular weight distribution D is 1.8-3.0, and the number-average molecular weight Mn is 8-40 x 104The mass percentage of vinyl of the polybutadiene block is 50-70%.
The block ratio of the solution polymerized styrene-butadiene rubber of the invention to styrene/butadiene (mass ratio) is (20-40)/(80-60).
The preferred number average molecular weight of the solution polymerized styrene-butadiene rubber is Mn 8-20 x 104。
The Mooney viscosity of the oil-filled crude rubber of the solution polymerized styrene-butadiene rubber is 55-65 after the rubber oil with the mesenchymal content of 27.3% is filled in the crude rubber, and the Mooney viscosity of the corresponding non-oil-filled crude rubber is 115-125.
The invention also provides application of the wide-distribution, high-elasticity and functionalized solution-polymerized styrene-butadiene rubber as an elastomer material applied to a tread rubber formula.
Preferably, the tread rubber formula comprises the following components in parts by mass: 100-130 parts of wide-distribution, high-elasticity and functionalized solution-polymerized styrene-butadiene rubber, 30-45 parts of BR, 100-120 parts of white carbon black GR, 20-60 parts of environment-friendly rubber filling oil, 2.7-3.0 parts of sulfur, 758-12 parts of Si-69/or silicon, 3307-10 parts of carbon black N, 2-3 parts of stearic acid, 4.5-5.0 parts of zinc oxide, 40101-2 parts of anti-aging agent, 2-3 parts of promoter CZ and 2-3 parts of promoter D.
The technical scheme of the invention adopts an anionic polymerization method, n-butyllithium is taken as an initiator, ethers are taken as vinyl unit activators, divinylbenzene is taken as a branching agent, a diazo reagent is taken as a regulator of molecular mass distribution, a polar compound is taken as an end-capping agent, and the mixture of styrene and butadiene is subjected to random copolymerization in a polymerization kettle taking cyclohexane as a solution to prepare the styrene butadiene rubber (F-SSBR for short) with a closed polar group end, high vinyl content, wide molecular weight distribution and high branching type solution polymerization.
The specific synthetic process of the solution polymerized styrene butadiene rubber provided by the invention comprises the following three steps of reaction:
the first step is as follows: adding cyclohexane or hexane or their mixture as solvent into a polymerization kettle, and then adding quantitative divinylbenzene, conjugated diene, ether activator and n-butyllithium respectively to initiate to generate di-lithium or poly-lithium oligomeric active lithium;
the second step is that: then adding a quantitative diazo reagent into a polymerization system, and then adding mixed styrene and butadiene for random copolymerization at one time, and the diazo reagent also belongs to Lewis base and has the effect of regulating 1, 2-addition;
the third step: after the monomer polymerization is finished, adding a quantitative polar active end-capping agent for end-capping reaction; finally, the glue solution is hydrolyzed and condensed to form raw glue.
The F-SSBR prepared by the invention is preferably used as a tire tread rubber in a formula of all-white carbon-filled silicon, and a small amount of carbon black is selected as a coloring agent. The specific formula (measured by mass parts) is as follows: 100-130 parts of SSBR, 30-45 parts of BR, 175GR 110 parts of white carbon black, 20-60 parts of environment-friendly rubber filling oil, 2.7-3.0 parts of sulfur, 758-12 parts of Si-69/or silicon-3, 7-10 parts of carbon black N3307, 2-3 parts of stearic acid, 4.5-5.0 parts of zinc oxide, 40101.5 parts of anti-aging agent, 2.7 parts of accelerator CZ and 2.3 parts of accelerator D.
The tread rubber mixing of the invention can be carried out by primarily mixing in an open mill or an internal mixer to form a mixing mill or master batch, and then the master batch is operated by a method known in the industries of rubber tapping, thinning, tabletting and the like on the open mill.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
aiming at the defects that the existing SSBR can not carry out end-capping modification on the end of a polymer molecule by adopting a continuous polymerization method or can introduce a polar group into a molecular chain by adopting an interrupted polymerization method, but the blocking rate of the polar group is not higher than 50%, the molecular mass distribution and the fraction are too low, the molecular mass distribution is too narrow, long and short branched chains in the molecule and the melt elasticity is too low, and the like.
The present invention has the technological scheme that random styrene-butadiene copolymer is prepared with diazo reagent, molecular chain branching reagent, vinyl unit regulator, end group blocking agent, etc. introduced into anionic polymer system. The blocking rate of the end functional groups of the molecular chain is more than 75%, the molecular mass distribution of the polymer is 1.8-3.0, the molecular chain with higher melt elasticity has long-short chain branching, and the content of vinyl units reaches up to 70%. Excellent processability and handling flexibility even in compounding, extrusion, sheeting, and molding units in higher tire formulations of high oil extended, fully filled white carbon black formulations. The purpose is to have intelligent mixing processing, and the manufactured tire further embodies a high-performance green tire with low rolling resistance and good wet skid resistance.
The F-SSBR has simple preparation process, mainly reflects that the polymerization reaction is stable and easy to control, has no implosion phenomenon, has all reaction units which are homogeneous reaction, has short polymerization period, can be completed by utilizing the existing mature discontinuous polymerization equipment, and is easy to industrialize.
Drawings
FIG. 1 is a temperature rise-time curve during the copolymerization reaction.
Detailed Description
The present invention is illustrated by the following examples, which are not intended to limit the scope or practice of the invention.
The number average molecular weight and molecular weight distribution index of the polymer were measured by Gel Permeation Chromatography (GPC) in the following examples; measuring the physical properties of the hot-melt tabletting adhesive by adopting an INSTRON tensile machine; the microstructure of the polymer was determined quantitatively by H-NMR spectroscopy.
Example 1
Adding 7000mL of n-hexane cyclohexane solution with the mass fraction of 10% into a 10-liter polymerization kettle under the protection of nitrogen, starting stirring, then adding 3mL of 99.0% tetrahydrofurfuryl alcohol ethyl ether ETE, 8mL of 0.8mol/L DVB cyclohexane solution, 4.0mL of isoprene and 16mL of 0.72mol/L NBL, heating to 52 ℃, and reacting for 15-20 min; and then adding 1.0mL of DBU, then adding 200mL of mixed monomer of styrene and 800mL of butadiene for a second-stage copolymerization reaction, wherein a temperature rise-time curve of the random copolymerization reaction is shown in figure 1, reacting for 28min after the polymerization temperature rises to the maximum temperature of 72 ℃, adding 12mL of N, N' -dimethyl imidazolidinone of 0.70mol/L into active glue solution in a polymerization kettle, and carrying out end-capping reaction for 25-30 min at 55-70 ℃ to obtain the polymer. Finally, discharging the glue solution, hydrolyzing, condensing and drying to obtain the F-SSBR crude glue.
The vinyl mass content of the butadiene segment in the F-SSBR molecule was determined by H-NMR spectroscopy to be 61.8%, the polymer number average molecular weight Mn was 86000 and the molecular weight distribution index D was 2.16 by Gel Permeation Chromatography (GPC); the Mooney viscosity ML of the dried raw rubber is 62.5.
Example 2
The relevant process conditions in example 1 were unchanged except that 0.8mL of DBU was added. Wherein the second-stage polymerization state is that the second-stage initial polymerization temperature is 53.5 ℃, the temperature rise time of the mixed monomer polymerization is 16min, the polymerization maximum temperature is 69.5 ℃, and the second-stage total polymerization time is 60 min; and then adding 15mL of 0.70mol/L N, N' -dimethylimidazolidinone into the active glue solution in the polymerization kettle, carrying out end-capping reaction for 20min at 55-60 ℃, and then adding 8mL of 0.70mol/L trimethylchlorosilane into the polymerization glue solution to carry out condensation reaction with lithium on the dimethylimidazolidinone for 15 min.
Discharging the glue solution, hydrolyzing, condensing and drying to obtain the F-SSBR crude glue. The vinyl mass content of the butadiene segment in the F-SSBR molecule was 60.4%, the polymer number average molecular weight Mn was 102700, the molecular weight distribution index D was 1.86, and the Mooney viscosity ML of the dried raw rubber was 60.4.
Example 3
The relevant process conditions in example 1 were unchanged except that 1.2mL of DBU, 10mL of DVB and 19mL of NBL were added. Wherein the second-stage polymerization state is that the second-stage initial polymerization temperature is 47.6 ℃, the temperature rise time of the mixed monomer polymerization is 20min, the polymerization maximum temperature is 66 ℃, and the total second-stage polymerization time is 70 min; then adding 15mL of N, N' -dimethyl imidazolidinone of 0.70mol/L into the active glue solution in the polymerization kettle, carrying out end-capping reaction for 20min at 66 ℃, and then adding 8mL of trimethyl monochlorosilane of 0.70mol/L into the polymerization glue solution to carry out condensation reaction for 15 min.
Discharging the glue solution, hydrolyzing, condensing and drying to obtain the F-SSBR crude glue. The vinyl mass content of the butadiene segment in the F-SSBR molecule is measured to be 66.4 percent, the polymer number average molecular weight Mn is 86300, the molecular weight distribution index D is 2.86, and the Mooney viscosity ML of the dried raw rubber is 57.7.
Example 4
The relevant process conditions in example 1 were unchanged except that 3.2mL of ETE, 1.0mL of DBN, 10mL of DVB, 18mL of NBL, 5mL of isoprene, 220mL of styrene, and 400mL of butadiene were added. Wherein the second-stage polymerization state is that the second-stage initial polymerization temperature is 57.2 ℃, the temperature rise time of the mixed monomer polymerization is 12min, the polymerization maximum temperature is 71 ℃, and the total second-stage polymerization time is 60 min; then adding 15mL of N, N' -dimethyl imidazolidinone of 0.70mol/L into the active glue solution in the polymerization kettle, carrying out end-capping reaction for 20min at 66 ℃, and then adding 10mL of trimethyl monochlorosilane of 0.70mol/L into the polymerization glue solution to carry out condensation reaction for 15 min.
Discharging the glue solution, hydrolyzing, condensing and drying to obtain the F-SSBR crude glue. The vinyl mass content of the butadiene segment in the F-SSBR molecule was 60.4%, the polymer number average molecular weight Mn was 81500, the molecular weight distribution index D was 1.78, and the Mooney viscosity ML of the dried raw rubber was 60.7.
Example 5
The relevant process conditions in example 1 were unchanged except that 0.6mL of DBU, 5mL of DVB and 10mL of NBL were added. Wherein the second-stage polymerization state is that the second-stage initial polymerization temperature is 53.3 ℃, the temperature rise time of the mixed monomer polymerization is 22min, the polymerization maximum temperature is 73 ℃, and the total second-stage polymerization time is 70 min; then adding 7mL of N, N' -dimethyl imidazolidinone of 0.70mol/L into the active glue solution in the polymerization kettle, carrying out end-capping reaction for 20min at 66 ℃, and then adding 6mL of tributyl monochlorotoxin of 0.70mol/L into the polymerization glue solution to carry out condensation reaction with lithium on the dimethyl imidazolidinone for 15 min.
Discharging the glue solution, hydrolyzing, condensing and drying to obtain the F-SSBR crude glue. The vinyl mass content of the butadiene segment in the F-SSBR molecule was measured to be 60.3%, the polymer number average molecular weight Mn was 185000, the molecular weight distribution index D was 2.66, and the Mooney viscosity ML of the dried raw rubber was 116.
Example 6
The relevant process conditions in example 1 were unchanged except that 0.5mL of DBN, 10mL of DVB, 9mL of NBL, 5mL of isoprene, 250mL of styrene, and 400mL of butadiene were added. Wherein the second-stage polymerization state is that the second-stage initial polymerization temperature is 53.8 ℃, the temperature rise time of the mixed monomer polymerization is 21min, the polymerization maximum temperature is 72 ℃, and the second-stage total polymerization time is 65 min; then adding 6mL of N, N' -dimethylimidazolidinone of 0.70mol/L into the active glue solution in the polymerization kettle, carrying out end-capping reaction for 20min at 66 ℃, and then adding 4mL of trimethylchlorosilane of 0.70mol/L into the polymerization glue solution to carry out condensation reaction for 15 min.
Discharging the glue solution, hydrolyzing, condensing and drying to obtain the F-SSBR crude glue. The vinyl mass content of the butadiene segment in the F-SSBR molecule was 63.2%, the polymer number average molecular weight Mn was 206400, the molecular weight distribution index D was 1.94, and the Mooney viscosity ML of the green rubber after drying was 122.
Comparative example 1
The relevant process conditions in example 1 were unchanged except that the amount of DBU added was 1.5 mL. Polymerization results: the second-stage heating time is 36min, the maximum temperature of the polymerization reaction is 66 ℃, and the total reaction time is 90 min. The polymer number average molecular weight Mn was 71500, the molecular weight distribution index D was 3.84, and the mooney viscosity ML of the green rubber after drying was 42.
Comparative example 2
The relevant process conditions in example 1 were unchanged except that the DBU added was 2.0 mL. Polymerization results: the initial temperature of the second stage is 48.1 ℃, and after the reaction is carried out for 22min, the temperature is not increased after the polymerization temperature is increased to 52 ℃, which indicates that the polymerization reaction is in a stop state.
Comparative example 3
The relevant process conditions in example 1 were unchanged except that 0.4mL of DBU was added. Polymerization results: the initial temperature of the second stage is 54 ℃, and the polymerization temperature is raised to 82.7 ℃ and then the reaction is carried out for 15min under the condition of heat removal by cold water in the reaction process of 4 min. The polymer was found to have Mn of 93500, a molecular weight distribution index D of 1.21 and a Mooney viscosity ML of 65.
Note: it can be seen from comparative examples 1 to 3 that the ratio of diazonium reagent to butyllithium molecule is too high or too low in the range defined in the present invention [ diazonium reagent/NBL (molar ratio): 1/(1.4 to 2.0) ], and neither the polymerization reaction nor the resulting polymer is satisfactory.
Application example 1
General solution polymerized styrene-butadiene rubber JSR563, SSBR2563-6 produced by the discontinuous process of the synthetic rubber division of the Middy and petrochemical company, and semi-functionalized solution polymerized styrene-butadiene rubber Y-031 produced by the discontinuous process of the Japan Asahi chemical company, and F-SSBR in examples 1 and 5 of the present invention were mixed, processed, vulcanized, molded and tabletted in a 1L internal mixer according to the white carbon black formula, respectively. The processing behavior and physical properties of the rubber are shown in Table 1.
TABLE 1 mixing behavior of different SSBR and physical Properties of the vulcanizates$
Injecting the formula (mass parts) of the tread rubber into SSBR (stabilized styrene butadiene rubber) 120; BR 40; white carbon black 175GR 105; carbon black N2358; silicon-6910; promoter CZ 2.7; accelerator D2.3; 4.8 of ZnO; 2.4 parts of stearic acid; an antioxidant 40101.5; wax 1; 2.4 of sulfur; TDAE rubber oil (wherein the oil content of the SSBR-2563 crude rubber is 27.3 wt%, the added oil in the formula is 22.2 parts by mass, and the other SSBR crude rubbers are non-oil-extended rubbers, and the added oil is 55 parts by mass.)
From the results in Table 1, it is found that the wide MWD high melt elasticity functionalized solution polymerized styrene butadiene rubber of the present invention exhibits excellent processability, low rolling resistance and high grip performance using a fully filled white carbon black formulation.
Claims (17)
1. A preparation method of wide-distribution, high-elasticity and functionalized solution-polymerized styrene-butadiene rubber is characterized by comprising the following steps: the method comprises the following steps:
1) adding divinyl benzene, conjugated diene and alkyl lithium initiator into the anionic polymerization solution system to carry out polymerization reaction;
2) sequentially adding a diazo reagent and a styrene/butadiene mixed monomer into an anionic polymerization solution system to perform random copolymerization reaction;
3) adding a polar end capping agent into an anionic polymerization solution system for end capping reaction, and then hydrolyzing and coagulating to obtain the product.
2. The method of claim 1, wherein the solution polymerized styrene-butadiene rubber has a broad distribution, high elasticity and functionalization, and the method comprises the following steps: the anionic polymerization solution system contains at least one active regulator selected from tetrahydrofuran, tetrahydrofurfuryl alcohol ethyl ether, ditetrahydrofurfuryl propane, tetrahydrofurfuryl amine and tetrahydrofurfuryl alcohol ether.
3. The method of claim 2, wherein the solution polymerized styrene-butadiene rubber has a broad distribution, high elasticity and functionalization, and the method comprises the following steps: the concentration of the activity regulator in an anion polymerization solution system is 250-450 mg/L.
4. The method of claim 1, wherein the solution polymerized styrene-butadiene rubber has a broad distribution, high elasticity and functionalization, and the method comprises the following steps:
the molar ratio of the divinyl benzene to the alkyl lithium initiator is 1 (2-3);
the dosage of the conjugated diene relative to the lithium alkyl initiator is 200-500 g/mol.
5. The method of claim 4, wherein the solution polymerized styrene-butadiene rubber has a broad distribution, high elasticity and functionalization, and the method comprises the following steps:
the divinyl benzene is a mixture containing o, m and p isomers;
the conjugated diene comprises butadiene and/or isoprene;
the alkyl lithium initiator is butyl lithium.
6. The method of claim 1, wherein the solution polymerized styrene-butadiene rubber has a broad distribution, high elasticity and functionalization, and the method comprises the following steps: the diazo reagent comprises 1, 5-diazobicyclo [4,3,0] -non-5-ene and/or 1, 8-diazobicyclo [5,4,0] -non-5-ene.
7. The method of claim 6, wherein the solution polymerized styrene-butadiene rubber has a broad distribution, high elasticity and functionalization, and the method comprises the following steps: the molar ratio of the diazo reagent to the alkyl lithium is 1 (1.4-2.0).
8. The method of claim 1, wherein the solution polymerized styrene-butadiene rubber has a broad distribution, high elasticity and functionalization, and the method comprises the following steps: the mass ratio of styrene to butadiene in the styrene/butadiene mixed monomer is (20-40)/(80-60).
9. The method of claim 1, wherein the solution polymerized styrene-butadiene rubber has a broad distribution, high elasticity and functionalization, and the method comprises the following steps: the polar end-capping reagent comprises at least one of chlorotrifluoromethane tin, chlorotrimethyl silicon, aminobenzophenone, N' -dimethyl imidazolidinone and organic acid ester.
10. The method of claim 9, wherein the solution polymerized styrene-butadiene rubber has a broad distribution, high elasticity and functionalization, and the method comprises the following steps: the molar ratio of the polar end-capping agent to the lithium alkyl is (0.7-1.0): 1.
11. The method of any one of claims 1 to 10, wherein the solution polymerized styrene-butadiene rubber with wide distribution, high elasticity and functionalization comprises: the temperature of the polymerization reaction is 50-60 ℃, the pressure is 0.3-0.5 MPa, and the time is 15-20 min.
12. The method of any one of claims 1 to 10, wherein the solution polymerized styrene-butadiene rubber with wide distribution, high elasticity and functionalization comprises: the initial temperature of the copolymerization reaction is 50-58 ℃, the pressure is 0.3-0.5 MPa, the highest temperature is less than 75 ℃, the temperature rise rate is controlled within the range of 1.0-1.3 ℃/min, the temperature rise time is 12-20 min, and the copolymerization reaction is carried out for 40-50 min under the adiabatic condition when the temperature reaches the highest temperature.
13. The method of any one of claims 1 to 10, wherein the solution polymerized styrene-butadiene rubber with wide distribution, high elasticity and functionalization comprises: the temperature of the end-capping reaction is 50-75 ℃, the pressure is 0.3-0.5 MPa, and the time is 20-25 min.
14. A wide distribution, high elasticity and functionalized solution polymerized styrene-butadiene rubber, which is characterized in that: the preparation method of any one of claims 1 to 13.
15. The solution-polymerized styrene-butadiene rubber with wide distribution, high elasticity and functionalization according to claim 14, wherein: a molecular weight distribution D of 1.8 to 3.0, a number average molecular weight Mn of 8 to 40 x 104The mass percentage of vinyl of the polybutadiene block is 50-70%.
16. Use of a broad distribution, high elasticity and functionalized solution polymerized styrene-butadiene rubber according to claim 14 or 15 wherein: the elastomer is used as an elastomer material for tread rubber formula.
17. The use of a broad distribution, high elasticity and functionalized solution polymerized styrene-butadiene rubber according to claim 16 wherein: the tread rubber formula comprises the following components in parts by mass: 100-130 parts of wide-distribution, high-elasticity and functionalized solution-polymerized styrene-butadiene rubber, 30-45 parts of BR, 100-120 parts of white carbon black (GR), 20-60 parts of environment-friendly rubber filling oil, 2.7-3.0 parts of sulfur, 758-12 parts of Si-69/or silicon, 3307-10 parts of carbon black N, 2-3 parts of stearic acid, 4.5-5.0 parts of zinc oxide, 40101-2 parts of anti-aging agent, 2-3 parts of promoter CZ and 2-3 parts of promoter D.
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| CN117487076A (en) * | 2023-12-29 | 2024-02-02 | 新疆独山子石油化工有限公司 | Wide-distribution modified solution polymerized styrene-butadiene rubber and preparation method thereof |
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| CN117567685A (en) * | 2024-01-16 | 2024-02-20 | 新疆独山子石油化工有限公司 | High-wear-resistance solution polymerized styrene-butadiene rubber and preparation method thereof |
| CN117567685B (en) * | 2024-01-16 | 2024-04-16 | 新疆独山子石油化工有限公司 | High-wear-resistance solution polymerized styrene-butadiene rubber and preparation method thereof |
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