CN112210040B - Wide-distribution polybutadiene-isoprene rubber and preparation method thereof - Google Patents
Wide-distribution polybutadiene-isoprene rubber and preparation method thereof Download PDFInfo
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- CN112210040B CN112210040B CN201910613162.5A CN201910613162A CN112210040B CN 112210040 B CN112210040 B CN 112210040B CN 201910613162 A CN201910613162 A CN 201910613162A CN 112210040 B CN112210040 B CN 112210040B
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- CN
- China
- Prior art keywords
- isoprene
- rubber
- polybutadiene
- distribution
- wide
- Prior art date
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- 238000009826 distribution Methods 0.000 title claims abstract description 84
- 229920003049 isoprene rubber Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920001971 elastomer Polymers 0.000 claims abstract description 111
- 239000005060 rubber Substances 0.000 claims abstract description 109
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 102
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 102
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 79
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 62
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 20
- 239000012954 diazonium Substances 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 16
- 239000005062 Polybutadiene Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 29
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 20
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229920002857 polybutadiene Polymers 0.000 claims description 14
- 230000000977 initiatory effect Effects 0.000 claims description 13
- 238000011925 1,2-addition Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- -1 alkyl lithium Chemical compound 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 230000003247 decreasing effect Effects 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 abstract description 33
- 244000043261 Hevea brasiliensis Species 0.000 abstract description 24
- 239000000178 monomer Substances 0.000 abstract description 24
- 229920003052 natural elastomer Polymers 0.000 abstract description 22
- 229920001194 natural rubber Polymers 0.000 abstract description 22
- 230000032683 aging Effects 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000005336 cracking Methods 0.000 abstract 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 32
- 239000006229 carbon black Substances 0.000 description 14
- 239000002131 composite material Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 239000004636 vulcanized rubber Substances 0.000 description 13
- 230000020169 heat generation Effects 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 229920006978 SSBR Polymers 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 9
- 238000007334 copolymerization reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 6
- 230000003712 anti-aging effect Effects 0.000 description 6
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 230000035882 stress Effects 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000005641 tunneling Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YJUUZFWMKJBVFJ-UHFFFAOYSA-N 1,3-dimethylimidazolidin-4-one Chemical compound CN1CN(C)C(=O)C1 YJUUZFWMKJBVFJ-UHFFFAOYSA-N 0.000 description 2
- 241001441571 Hiodontidae Species 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000006085 branching agent Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000012718 coordination polymerization Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical class [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000007156 chain growth polymerization reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000012967 coordination catalyst Substances 0.000 description 1
- 239000002633 crown compound Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- FRJXTXHUSWZJDY-UHFFFAOYSA-M hexane;tributyl(chloro)stannane Chemical compound CCCCCC.CCCC[Sn](Cl)(CCCC)CCCC FRJXTXHUSWZJDY-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 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
- C08F236/06—Butadiene
-
- 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
-
- 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
- B60C1/0025—Compositions of the sidewalls
-
- 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
- C08F236/08—Isoprene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a wide-distribution polybutadiene-isoprene rubber and a preparation method thereof. Butadiene and isoprene are used as polymerization monomers, divinylbenzene is used as a widening agent for improving weight average molecular mass and molecular weight distribution, a diazonium reagent is used as a regulator for improving the molecular mass distribution of the polymer, lithium-based catalytic polymerization is adopted and a polar end capping agent is used for end capping, so that polybutadiene-isoprene rubber with trans-1, 4 addition product content higher than 75% and polyisoprene blocks with chain lengths distributed in a gradient manner is prepared; the copolymer rubber has wide molecular mass distribution, high melt elasticity and good processability; the rubber is suitable for tire treads, sidewalls, inner liners and belt layers, and particularly has excellent compatibility, cracking resistance and aging resistance when being compounded with natural rubber.
Description
Technical Field
The invention relates to polybutadiene-isoprene rubber, in particular to polybutadiene-isoprene rubber which is synthesized by lithium catalysis and has the characteristics of wide molecular weight distribution, polyisoprene block with chain length in gradient distribution, high trans-T-1, 4 addition ratio and the like, and is particularly suitable for tire treads, sidewalls, inner liners and belt ply rubber, and belongs to the field of tire rubber.
Background
BR-9000 in the prior art is a common tire sizing material, but has Tg= -100 ℃, regular polymer molecular chain height and strong crystallization tendency, starts to harden at minus 35 ℃ and easily loses elasticity, and the rubber for the belt layer, the sidewall and other parts of the tire is usually used together with BR, so that the prepared tire is easy to crack due to incompatibility of the Natural Rubber (NR) and BR, and the service life of the tire is influenced.
The trans-butadiene-isoprene rubber (TBIR) has lower crystallization melting point and crystallinity, lower TIR and obviously improved processability, is a novel elastomer material, and can be widely used for tire treads, sidewalls, inner liners and belt ply rubbers.
The catalyst system used for preparing polybutadiene-isoprene (BIR) rubber comprises transition metal, lithium system, rare earth and the like. TBIR prepared by the Ti-Mg coordination catalyst system has low compression heat generation, fatigue resistance, tear resistance, wear resistance and low noise, and the raw rubber strength is also very outstanding, so that the TBIR is an ideal rubber material for high-performance tires, and the defects are that the monomer conversion rate is less than 70 percent and the self-adhesion of raw rubber is low; in the existing lithium-based catalysis in BIR synthesis, as the polymerization temperature increases, butyl is reactedThe 1, 4-addition content of diene and isoprene is increased, the content of 1, 2-and 3, 4-addition products is reduced, but the molecular mass distribution of the polymer is too narrow, the raw rubber strength is low, the cold flow is large, the processability is poor, and the like. As described in US5405927, isoprene-butadiene copolymers synthesized by organolithium/barium salt catalysis, the melting point of the copolymer decreases with increasing isoprene content in the monomer and can be stretch crystallized, thus increasing the green strength and tackiness, which is suitable for tread compounds for tires. In addition, british patent GB2029426 and US4413089 describe random or block copolymers obtained by copolymerizing butadiene and isoprene catalyzed by barium salt-tributyl magnesium lithium/trialkyl aluminum, which have a mooney viscosity of 59, a molecular weight distribution d=1.46, and good processability and green tack of the polymer, and can be used in combination with natural rubber NR. EP629640 reports that the cis-form content of both monomers can reach more than 96% by adopting rare earth to catalyze the copolymerization of butadiene and isoprene, and that the two monomers are ideal random copolymerization, r in the system bd ＝1.09，r Ip =1.32, the ratio of the two ratios is close to 1, the Tg of the polymer is-73 ℃. Chinese patent CN105985487a discloses a butadiene-isoprene copolymer rubber modified by functionalization at both ends of a macromolecular chain, and uses a functionalization initiator and a capping agent to share, so that both ends of the molecular chain contain different functional groups and have good binding force with carbon black/white carbon black, so that the copolymer rubber can effectively participate in elastic recovery of the whole cross-linking network, reduce energy loss in periodic deformation, improve heat generation and rolling resistance, but the functionalization initiator is unstable, easy to inactivate, difficult to prepare and the like. Chinese patent CN103387641A describes a trans-1, 4-structure butadiene-isoprene copolymer rubber and a preparation method thereof, in particular MgCl 2 A Ziegler-Natta catalyst system consisting of supported titanium and an organic aluminum compound catalyzes butadiene and isoprene to synthesize butadiene-isoprene copolymer rubber with a trans-1, 4-structure of more than 90%, wherein the copolymer rubber consists of 20-99.5% of isoprene units and 0.5-80% of butadiene units in a mole fraction. The preparation process of the trans-copolymerized rubber includes fixing the feeding ratio of butadiene to isoprene and catalyzing butadiene at 0-90 deg.cThe trans-copolymerized rubber formed by copolymerization of alkene and isoprene in a bulk and synthetic gradient mode has the characteristics of low heat generation, good wear resistance, flex fatigue resistance and the like, and is suitable for dynamic use of rubber products. Chinese patent CN106699966a provides a butadiene-isoprene copolymer rubber and a preparation method thereof, specifically discloses that the molecular chain of the copolymer rubber is composed of a butadiene homopolymerization section and a butadiene-isoprene random copolymerization section, the number average molecular weight of the butadiene homopolymerization section is 5 ten thousand-30 ten thousand, the content of cis-1, 4-structure in the butadiene homopolymerization section is not less than 97mol%, and the number average molecular weight of the butadiene-isoprene random copolymerization section is 5 ten thousand-50 ten thousand. The butadiene-isoprene copolymer rubber provided has excellent mechanical strength and flex crack resistance.
In the "effect of conversion on high trans-1, 4-butadiene-isoprene rubber Properties" petrochemical industry, 2010, 03), H was studied at different conversions 2 TiCl under adjustment 4 /MgCl 2 The supported catalyst is used for catalyzing and synthesizing the structure and the performance of high trans-1, 4-butadiene-isoprene rubber (TBIR). The results show that: the TBIR generated at the initial stage of polymerization has a longer sequence 1, 4-butadiene (Bd) unit structure, and the length of an isoprene (Ip) segment in the TBIR increases with the increase of the conversion rate. When the Mooney viscosities are similar, the green strength, elongation at break and tensile set of the TBIR all increase with increasing conversion, and the abrasion and rebound resilience of the TBIR vulcanizate Akron increase with increasing conversion. However, as the monomer conversion increases, the wet skid resistance of the TBIR vulcanizate decreases and heat generation increases. When the initial feeding ratio n (Bd) is n (Ip) =0.25, the comprehensive performance of the TBIR vulcanized rubber is optimal when the conversion rate is controlled to be 55% -65%. The TBIR is applied to the tire bead filler in the text of structural characterization of high trans-1, 4-butadiene-isoprene copolymer rubber and application research of the high trans-1, 4-butadiene-isoprene copolymer rubber in the tire bead filler of a car, high molecular report, 2015.12 (12 phase), so that the mixing cement crystallinity, the green strength and the hardness can be increased, and the vulcanization speed is accelerated; other properties of the blending vulcanized rubber containing TBIR are kept unchanged, compression temperature rise is obviously reduced, and wear resistance and ageing resistance are obviously improved; the compatibility of TBIR and NR is superior to BR. The results indicate NR and TBIRAfter that, the dispersibility of carbon black in the vulcanized rubber is better, about 20 parts of TBIR is applied to the radial tire bead filler of the car, other mechanical properties are kept at a higher level, and meanwhile, the wear resistance, the flex resistance and the ageing resistance are obviously improved, and the compression temperature rise is obviously reduced. The use of a new generation of synthetic rubber-trans-1, 4-butadiene-isoprene copolymer rubber (TBIR) in high performance car tire tread stock (solution polymerized styrene butadiene rubber/butadiene rubber, SSBR/BR) and the structure and properties of SSBR/BR/TBIR blends are described in the "Structure and Properties of Trans-1, 4-butadiene-isoprene copolymer rubber modified high performance car tire tread stock" high molecular report, 2018, 03. The results show that: TBIR exhibits higher green strength, modulus and toughness due to certain crystallinity relative to amorphous SSBR and BR. 10-20 parts of TBIR and SSBR/BR are used for modification, 30 parts of carbon black and 45 parts of white carbon black are added simultaneously, the green strength and the stretching stress of the SSBR/BR/TBIR rubber compound are improved, the scorch time (tc 10) and the normal vulcanization time (tc 90) are basically kept unchanged, the vulcanized rubber of the SSBR/BR/TBIR rubber compound is excellent in physical and mechanical properties, the tensile fatigue resistance is improved by 4.6-6.3 times, the compression strength is improved by 21.4-23.1%, the wear resistance is improved by 10.8-15.1%, the wet skid resistance is improved by 13.6-40.4%, and the rolling resistance is kept unchanged. Compared with SSBR/BR vulcanized rubber, the dispersion degree of the SSBR/BR/TBIR vulcanized rubber filler is improved by 7.3-14.9%, and the average size of the filler aggregate is reduced by 1.4-2.7 mu m. The high green rubber strength and modulus of the crystallizable TBIR can obviously inhibit aggregation of the filler in the rubber compound, improve the dispersibility of the filler in the vulcanized rubber, and finally contribute to the excellent performances of tensile fatigue resistance, high wear resistance, wet skid resistance, compressive strength, tensile modulus and the like of the SSBR/BR/TBIR vulcanized rubber, and the TBIR is an ideal novel synthetic rubber applied to the tread rubber of the high-performance car tire. In addition, the effect of the relative molecular mass (mooney viscosity) and its distribution on the trans 1, 4-butadiene-isoprene copolymer rubber (TBIR) properties was studied in the rubber industry, stage 12 2010, in the "effect of the relative molecular mass and its distribution on the high trans 1, 4-butadiene-isoprene copolymer rubber properties". The results show that: the plasticating and mixing performance of TBIR gradually improves along with the reduction of the Mooney viscosityTBIR mixing difficulty of more than 60 is increased, and processability is deteriorated; the comprehensive physical properties of TBIR are improved along with the increase of the Mooney viscosity, but the improvement effect of the physical properties and dynamic properties of the rubber material is not obvious after the Mooney viscosity is more than 55, and the comprehensive properties of the TBIR rubber material are optimal when the Mooney viscosity is 50-60. The tensile property, abrasion property and heat generating property of TBIR raw rubber and vulcanized rubber which are bimodal relative to molecular mass distribution are better; the flexural resistance of TBIR vulcanized rubber with unimodal molecular mass distribution is greatly improved.
The trans-1, 4-TBIR breaks the structural regularity of the TPI main chain, the crystallinity is obviously reduced, the radial tire belt layer is positioned at the base of the tire, plays a role in tightening the tire body and relieving impact, is a main stress part of the tire, and has the characteristics of good adhesion with steel wires, ageing resistance, low rolling resistance and the like, and the traditional belt layer formula adopts NR as a matrix.
Goodyear reported a high performance tire crown compound containing TBIR, which has a tunneling fatigue resistance of 10 to 100 times that of NR/BR, and is particularly suitable for sidewalls and bead portions having high tunneling fatigue resistance.
Document (HeAihua, polym. Sci.2003,89 (7): 1800-1807) reports that, in the case of a coordination polymerization system, butadiene-isoprene is copolymerized, since butadiene contains two front rails, and isoprene is affected by side methyl steric hindrance, the polymerization rate of butadiene is r (Bd) Ratio of polymerization of isoprene r=5.7 (IP) =0.17; in addition, the Qingdao university of science and technology research shows that the length of the IP chain link in TBIR increases with the increase of the conversion rate, and when the conversion rate is 55-65%, the TBIR is mainly based on the long-chain segment IP. The rubber has high rubber strength, elongation at break and deformation, and the comprehensive performance is optimal. The TBIR synthesis technology is produced by Shandong Dongying Gerui rubber and plastic New Material Co.
In Zhang Jianguo et al ("application of high-ethylene solution-polymerized styrene-butadiene rubber in high-performance tread rubber", "elastomer", 2013, 23 (3): 53-58.) "it is described that the butadiene unit 1, 2-adduct in lithium-based polymerized styrene-butadiene rubber is 62 to 68%, the cis-1, 4 adduct is 6 to 8%, and the trans-T-1, 4 adduct content is 26 to 32%. That is, the content of trans-1, 4-adducts in the polymer obtained by the traditional lithium-catalyzed polymerization of butadiene or isoprene under the regulation of an efficient activator is not higher than 40%.
In US 4451576, it is described that the use of diazonium compounds as regulators, butyl lithium initiates the preparation of polymers with a broad molecular mass distribution of butadiene or butadiene-styrene mixtures, which results in a butadiene polymerization conversion of 100%, a styrene conversion of 80%, a molecular mass distribution index of up to 7 or more, a polymer with a broad molecular embodiment, no branching, low elasticity, low heat generation of the compound mix, and is unsuitable for use in high performance tire silicone formulations; in addition, when the amount of the diazonium compound is more than 1.5 times that of butyllithium, the polymerization rate is extremely slow, and even the monomer is not polymerized.
In summary, the monomer conversion rate of the high trans-1, 4-butadiene-isoprene rubber (TBIR) catalyzed by the coordination supported catalyst is not higher than 65%, but if the monomer conversion rate is improved, the wet skid resistance of the TBIR vulcanized rubber is reduced, the heat generation is increased, and the processability is poor, which is not in accordance with the development requirement of the current high-performance green tire. While studies on trans-polybutadiene-isoprene rubber (BIR) with a block distribution and with a higher content prepared by lithium-based polymerization are not widespread.
Disclosure of Invention
In order to overcome the defects that the existing composite material with high cis BR and NR is poor in performance, the molecular weight distribution of BR synthesized by lithium catalysis is too narrow, the processability is poor, the content of T-1,4 is low and crystallization is easy; and the existing TBIR has the defects of poor raw rubber processability and the like, and the first aim of the invention is to provide the wide-distribution polybutadiene-isoprene rubber with low branched chain content, high trans-1, 4 addition unit content, wide molecular mass distribution, branched molecular chain length and ordered gradient distribution; the content of 1, 2-addition units of butadiene and 3, 4-addition units of isoprene in the wide-distribution polybutadiene-isoprene rubber are less than 10%, and the content of trans-1, 4 (T-1, 4) addition units of polyisoprene and polybutadiene units is higher than 75%, so that the strength of the polymer rubber is improved, the base crystallinity is reduced, the processability of the polymer rubber is improved, the polymer rubber is compatible with natural rubber and used for radial tire treads, sidewalls, inner liners and belt layers, the compatibility of the polymer rubber and the rubber is good, the ageing resistance and crack resistance of a composite material are enhanced, the stress and buffer impact resistance of a tire body are improved, and the rolling resistance of the tire is reduced; in particular, the composite sizing material has the characteristics of good adhesion with steel wires, aging resistance, digging and winding fatigue resistance and the like, replaces BR in the traditional belt layer formula or the existing TBIR (the defect that the matrix prepared by compounding is easy to age and crack due to poor compatibility of BR and NR), and can be used as a base material of a high-performance green tire.
The second object of the invention is to provide a method for preparing butadiene-isoprene rubber with wide molecular weight distribution and gradient blocks by lithium catalysis, wherein butadiene and isoprene are used as monomer raw materials, diazonium reagent is used as a mass distribution grade regulator, divinylbenzene is used as a chain extender, and the butadiene-isoprene rubber with the gradient blocks prepared by the method has micro blocks with high branching, wide molecular weight distribution and ordered gradient distribution and butadiene and isoprene units with higher block chains, is suitable for being used with natural rubber and used for radial tire treads, sidewalls, inner liners and belt plies, and particularly has the characteristics of good adhesion with steel wires, ageing resistance, tunneling fatigue resistance and the like. The synthesis method of the butadiene-isoprene rubber containing the gradient blocks is simple and mature in operation, low in cost and beneficial to industrial production.
In order to achieve the above technical object, the present invention provides a wide-distribution polybutadiene-isoprene rubber having the following expression;
R—B 1 I m B 2 I m-1 ……B m-1 I 2 B m I 1 D—F
wherein,
r is an initiator residue;
m is the number of micro blocks (m is a positive integer greater than 1);
B 1 ……B m is m butadiene homo-blocks and is composed of B 1 To B m The chain length of the butadiene homo-polymer block of (2) is gradually decreased;
I 1 ……I m is m isoprene homo-blocks and is represented by I 1 To I m The chain length of the isoprene homopolymerization block of the (B) is gradually decreased in a gradient manner;
d is a divinylbenzene branching unit having an average degree of branching of 1 to 2.5 (degree of branching may be random 0,1,2,3, …);
f is a polar end capping group;
the number average molecular weight Mn=15 to 25×10 of the broad distribution polybutadiene-isoprene rubber 4 The molecular mass distribution index is 2.5-3.5.
In a preferred embodiment, the ratio of the number of 1, 2-addition units of butadiene to the number of 3, 4-addition units of isoprene in the widely distributed polybutadiene-isoprene rubber is less than 10%, and the ratio of the number of trans-1, 4-addition units of polyisoprene to polybutadiene units is greater than 75%.
In a preferred embodiment, the raw mooney viscosity ml=50 to 70 of the broad distribution polybutadiene-isoprene rubber.
Preferably, R is an initiator residue such as n-butyl, isobutyl, etc.
In the wide-distribution polybutadiene-isoprene rubber, the chain length of the butadiene homo-block and the chain length of the isoprene homo-block in each branched long-chain molecule are different, the different sum values determine the molecular mass of a branched chain segment, and meanwhile, the polymer has different molecular mass distribution and distribution fractions.
The invention also provides a preparation method of the wide-distribution polybutadiene-isoprene rubber, which comprises the steps of adding a diazonium reagent, butadiene and isoprene into an anionic polymerization solution system, heating to an initiation temperature, adding alkyl lithium into the anionic polymerization solution system to initiate polymerization reaction, and continuously and slowly adding divinylbenzene into the anionic polymerization solution system in the polymerization reaction process; and after the polymerization reaction is finished, adding a polar end-capping agent into the anionic polymerization solution system to carry out end-capping reaction, thus obtaining the polymer.
In a preferred scheme, the mass ratio of butadiene to isoprene is (20-80): 80-20.
In a preferred embodiment, the molar ratio of divinylbenzene to alkyllithium is from 1.0 to 3.0:1; wherein the total monomer mass and the number of molecular masses of the alkyllithium determine the number average molecular mass Mn of the polymer.
In a preferred embodiment, the divinylbenzene is 0.08 to 0.16% of the total mass of butadiene and isoprene. Among them, divinylbenzene (DVB) is used as a branching agent for long and short chain molecules of a broad distribution polybutadiene-isoprene rubber.
Preferably, the diazonium reagent is preferably 1.5-diazoniabicyclo [4,3,0]]-5-nonene (DBN) or 1, 8-diazobicyclo [5,4,0]]One or a mixture of 7-undecene (DBU), preferably diazonium reagent/NBL (molecular ratio) =0.5-1.6, more preferably diazonium reagent/NBL (molecular ratio) =0.8-1.3, and the hindered amine diazonium reagent is combined with butyl lithium or active polymer lithium chain, so that the rapid initiation and the rapid growth of a lithium-based anionic polymerization monomer can be effectively prevented, the molecular mass distribution of the polymer is widened, the DVB branching effect for active chain growth of the polymer is added to improve the weight average molecular mass of the polymer, and the molecular mass distribution index M of the polymer is constructed under the combined action of the diazonium reagent and DVB W Mn=2.5 to 3.5, thereby improving the processability of the polymer raw rubber.
In a preferred embodiment, the molar ratio of diazonium reagent to alkyllithium is from (0.5 to 1.6): 1. The alkyl lithium is preferably butyl lithium.
Preferably, the initiation temperature and the polymerization reaction are in the range of 50 to 100 ℃. The preferred polymerization temperature is 80 to 100 ℃, and higher polymerization temperatures are advantageous for increasing the rate of trans-1, 4 addition and decreasing the ratio of 1, 2-addition to 1, 3-addition.
In a preferred embodiment, the anionic polymerization solution system contains at least one solvent selected from benzene, toluene, cyclohexane and n-hexane. N-hexane is preferred.
In a preferred scheme, the time for continuously adding the divinylbenzene into the anionic polymerization solution system is controlled within the range of 40-80 min, and the polymerization reaction is continued for 20-30 min after the divinylbenzene is added. In the synthesis process of the wide-distribution polybutadiene-isoprene rubber, NBL can be continuously added into a dilute solution of DVB after being added into a polymerization kettle once, and the preferable feeding time of DVB continuously added into the polymerization kettle is 50-60 min; after the DVB is added, the reaction is continued for 20 to 30 minutes at a temperature of preferably 90 to 95 ℃ so as to ensure that a small amount of isoprene in the late-stage polymer is completely converted.
Preferably, the divinylbenzene is added as a dilute solution after dilution with a solvent. The diluent is generally a polymerization solvent. The purpose of dilution is to control the slow addition of divinylbenzene, the degree of dilution being adjustable according to the actual situation.
Preferably, the polar capping agent comprises at least one element selected from tin, nitrogen, oxygen and silicon, and at least one functional group selected from halogen, ketone, acid, amine or ester capable of reacting with active lithium. The polar end-capping agent of the present invention is a polar end-capping agent commonly found in the prior art. The polar end-capping agent is preferably at least one or more of tributyl tin chloride, N' -dimethylimidazolidinone, trimethylchlorosilane and other organic matters containing tin, nitrogen, oxygen, silicon, sulfur and other atoms, halogen, ketone, acid or esters and the like and capable of being added or condensed with active lithium; most preferably, one of N, N '-dimethylimidazolidinone and tributyltin monochloride, or most preferably, N' -dimethylimidazolidinone molecules are added with active chain lithium to form [ -O - Li + ]Then tributyltin chloride and O are used again - Li + Condensation blocking is carried out, and the capping reagent is preferably added in an amount equal to the molecular mass of active lithium.
In a preferred scheme, the temperature of the end capping reaction is 50-90 ℃ and the time is 15-20 min.
The invention adopts an anion polymerization method, n-butyllithium is used as an initiator, a trace amount of diazonium reagent is used as a molecular mass distribution widening agent, divinylbenzene is used as a molecular chain branching agent and a regulator for improving the weight average molecular mass of a polymer, a polar compound is used as a blocking agent, a mixture of butadiene, isoprene and trace amount of divinylbenzene is subjected to random copolymerization in a polymerization kettle using hexane as a solvent, and finally the prepared copolymerization glue solution containing active lithium is blocked at the tail end by using polar groups, so that the polybutadiene-isoprene rubber with wide distribution, which has the advantages of low content of vinyl and polyisoprene 3, 4-addition units of polybutadiene segments, high trans-1, 4-addition unit content, wide molecular mass distribution and ordered gradient distribution of molecular chain length branching, is obtained.
The synthesis method of the wide-distribution polybutadiene-isoprene rubber comprises the following specific steps:
1) Polymerization reaction: adding quantitative solvent and diazo reagent into a polymerization kettle, then adding quantitative butadiene and isoprene into the polymerization kettle at the same time, starting stirring, heating the material in the polymerization kettle to the polymerization initiation temperature by using hot water, at the moment, adding quantitative n-butyllithium for monomer initiation and chain growth polymerization reaction at one time, wherein the time required for the polymerization reaction from the initiation temperature to the highest polymerization temperature is 40-50 min, so that the dilute hexane solution of divinylbenzene is required to be continuously added during the polymerization reaction and chain growth, the continuous feeding time of the dilute hexane solution is 40-60 min, and the reaction is continued for 20-30 min after the divinylbenzene is added.
2) End-capping reaction: after the polymerization reaction is finished, adding a quantitative polar compound capable of condensing with the polyisoprene active lithium at the tail end of the polymer molecular chain into a polymerization kettle for end-capping reaction, wherein the reaction time is 15-20 min.
3) And (5) condensing and drying: and removing the polymerized glue solution from the polymerization kettle, adding necessary antioxidant, uniformly mixing, condensing by water vapor, and drying to obtain the raw glue.
The diazonium reagent adopted by the invention is hindered amine miaow which has the characteristics of Lewis base, and the hindered amine miaow is not only a regulator of microstructure of lithium polymer, but also a retarder for initiating and polymerizing chain growth by active lithium, namely, the polymerization rate of butadiene or isoprene can be delayed, the purposes that two monomers of butadiene and isoprene are slowly initiated and active chains initiated are slowly grown are achieved, and in the anionic polymerization system, the inhibition or delay of the diazonium reagent to active lithium is random, and the molecular mass of the synthesized polymer is finally provided with wide molecular fraction and wide molecular mass distribution. In addition, in the continuous addition of the divinylbenzene into the polymerization system, the divinylbenzene plays a role of slow branching and long chain branching, the weight average molecular mass of the polymer can be improved, the molecular mass distribution and the distribution fraction of the copolymer are further widened, the melt elasticity and the raw rubber strength of the copolymer are increased, and the subsequent processing of the raw rubber is facilitated. It should be further described that the electron cloud distribution in the molecular structure of divinylbenzene has a much higher polymerization rate than butadiene and isoprene, so that divinylbenzene is not suitable to be added to the initiation or polymerization environment at one time, or divinylbenzene can be rapidly homo-polymerized or aggregated, and the purposes of branching and widening the molecular mass of the copolymer cannot be achieved.
What needs to be further explained is: butadiene is known to those skilled in the art to have a greater polymerization rate than isoprene under normal lithium-based catalysis, and is known in the literature ("research on copolymerization of tetrahydrofuran as a regulator and isoprene", any brilliant, etc., polymer materials of university of major engineering). Describes the rate of polymerization r when THF/NBL=0.5 Bd ＝2.08，r Ip =0.39, r as the THF usage increases Bd Continue to increase, r Ip And continuing to decrease. In addition, it is reported in U.S. patent No. 4451576 that butadiene can be fully converted by the diazonium reagent, while the conversion of styrene is no higher than 81%. In the polymerization environment of the diazonium reagent of the present invention, it was unexpectedly found that when the molecular ratio of diazonium reagent/NBL (butyllithium) is about 1.4:1, equal mass of butadiene and isoprene are polymerized at 85-95℃respectively, and when the polymerization time is 75min, butadiene can be completely converted, while the conversion of isoprene is 87.4%; when the polymerization time was 90min, isoprene was converted completely. I.e.butadiene in the polymerization system of the invention has a greater polymerization rate than isoprene. That is, most of butadiene is initiated and chain extended first in the earlier stage of polymerization, only a small amount of isoprene is initiated, and when the relative concentration of butadiene is lower and the relative concentration of isoprene is higher in the later stage of copolymerization, the front section of the molecular chain of the copolymer is mainly the block of polybutadiene and a small amount of isoprene is randomly copolymerized with a large amount of butadiene to form a higher block unit of polybutadiene and a trace amount of butadieneA lower polyisoprene micro-block unit; in the latter stages of the polymerization, the molecular chain end segments of the copolymers are predominantly the longer homo-block units of polyisoprene. Namely, the butadiene-isoprene copolymer of the invention belongs to gradient-containing block copolymers which are orderly and gradiently distributed. Copolymers of such molecular configuration are beneficial for compatibility with natural rubber.
The broad distribution polybutadiene-isoprene copolymers of the present invention have some molecular chains that are free of divinylbenzene branching units and some molecular chains that contain multiple branching units.
The preparation of the broad distribution polybutadiene-isoprene copolymer according to the present invention does not require the use of Lewis bases as activators.
In the preparation process of the wide-distribution polybutadiene-isoprene copolymer rubber, the feeding ratio of butadiene, isoprene and divinylbenzene is fixed, the mixed monomer is initiated by butyl lithium in a carbon hydrocarbon solution, the reaction has the characteristics of continuous initiation, chain extension and long-short chain irregular branching, 1, 2-addition and 3, 4-addition in the monomer chain extension are low, trans-1, 4-addition is high, and the polybutadiene micro block and polyisoprene micro block are formed by gradient distribution in the copolymer molecular chain.
The invention also provides application of the wide-distribution polybutadiene-isoprene rubber, which is compounded with NR and used for tire tread rubber, sidewall rubber, inner liner rubber or belt rubber.
The formula of the rubber for the tire tread base comprises the following components in parts by mass: 50 to 80 parts of NR, 20 to 50 parts of wide-distribution polybutadiene-isoprene rubber, 30 to 40 parts of carbon black, 15 to 25 parts of rubber softening oil, 10 to 20 parts of white carbon black, 2.0 to 3.0 parts of silane coupling agent, 3.0 to 4.0 parts of zinc oxide, 1.5 to 2.0 parts of stearic acid, 2.0 to 3.0 parts of anti-aging agent, 2.0 to 4.0 parts of accelerator and 3.0 to 3.4 parts of sulfur.
The tire sidewall rubber material formula comprises the following components in parts by mass: 30-60 parts of NR (non-aqueous polyurethane), 30-60 parts of wide-distribution polybutadiene-isoprene rubber, 40-70 parts of carbon black, 10-13 parts of rubber softening oil, 2-3 parts of tackifying resin, 10-20 parts of white carbon black, 2.0-3.0 parts of silane coupling agent, 1.0-2.0 parts of protective wax, 2.0-4.0 parts of zinc oxide, 1.5-2.5 parts of stearic acid, 2.0-3.0 parts of anti-aging agent, 2.0-4.0 parts of accelerator and 1.3-1.8 parts of sulfur.
In the above formulation, the auxiliary agent and auxiliary materials are all selected as usual in the art, and the silane coupling agent is Si-69 and/or Si-75. Rubber softening oil such as TDAE, NAP-10 and A1220 obtained by hydrofining heavy aromatic oil. White carbon black such as ZEOSIL1165. Accelerators such as accelerator NS and accelerator CZ. The tackifying resin is octyl phenolic tackifying resin.
The preparation method of the wide-distribution polybutadiene-isoprene rubber for radial tire rubber material comprises the following steps:
firstly, putting other raw materials except sulfur into an internal mixer for mixing, heating the mixed rubber under the shearing and friction actions of a rotor of the internal mixer, mixing for 90 seconds after the temperature of the mixed rubber is increased to 130-150 ℃, and discharging the composite rubber to form master batch. Putting the master batch into an open mill at 50-60 ℃, adding sulfur for mixing, cutting the left and right sides by 3/4 of a cutter for three times, adjusting the interval between each cutter to be 15s, adjusting the roll spacing to 0.8mm, alternately longitudinally thinning six times from each end, and pressing the sizing material into a film with the thickness of about 2.2mm, namely blanking, preparing a sample for vulcanization; the vulcanization of the rubber compound at the base of the tire is carried out according to the process conditions well known in the industry, namely, the vulcanization is carried out for 15min at 165 ℃. And (5) carrying out physical property analysis on the formed vulcanized rubber.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
compared with the existing composite material with the complex of high cis BR and NR, the existing composite material has the defects of poor processability, low content of T-1,4 addition units, easy crystallization, low monomer conversion rate, poor raw rubber processability with high viscosity and the like caused by the fact that the molecular weight distribution of the BR synthesized by lithium catalysis is too narrow. Compared with the prior art, the wide-distribution polybutadiene-isoprene copolymer rubber prepared by the lithium-based anionic polymerization method has the advantages of complete monomer conversion, high trans-1, 4 structure content in raw rubber molecules, low 1, 2-addition and 3, 4-addition unit content, long chain branching of raw rubber molecules, improved weight average molecular weight, wide molecular mass distribution of polymers, high melt elasticity, high raw rubber strength, balanced viscosity and elasticity, good processability and the like. In addition, nitrogen or/and tin atom composition groups with larger polarity are introduced at the tail ends of the raw rubber molecular chains of the polymer, the terminal closure rate is higher than 50%, so that a composite material formed by raw rubber and other rubber types is easy to disperse in mixing with carbon black, payne effect of vulcanized tread rubber of the composite material is reduced, meanwhile, the polar functional groups also shorten the length and concentration of an inert unit from a final crosslinking point of vulcanized network macromolecules to chain ends, and increase effective elastic recovery of macromolecules, thus energy generated in periodic deformation is easy to be converted into stored energy, and heat generation and hysteresis loss of tires are reduced.
The wide distribution polybutadiene-isoprene copolymer rubber of the invention can be used for tire tread, tread base, sidewall or inner liner rubber; particularly, the rubber has good compatibility with natural rubber NR, can replace BR in the traditional formula, strengthens the ageing resistance and crack resistance of the vulcanized composite material, improves the stress and buffer impact resistance of a tire body, and reduces the rolling resistance and dynamic heat generation of the tire; the composite sizing material composed of the wide-distribution polybutadiene-isoprene copolymer rubber and NR also has the characteristics of good adhesion with steel wires, aging resistance, digging and winding fatigue resistance and the like. Is an important raw material of high-performance green tires.
The reaction in the preparation of the wide-distribution polybutadiene-isoprene copolymer rubber belongs to homogeneous reaction, the preparation process is simple, the wide-distribution polybutadiene-isoprene copolymer rubber can be synthesized by utilizing the existing mature process, the reaction is easy to control and industrialize, the production cost is low compared with the TBIR prepared by a coordination polymerization system, and the recovery of the excess monomer which is not converted in the preparation of the TBIR is not required.
Detailed Description
The following examples illustrate the invention and are not to be construed as limiting the scope or practice of the invention.
The number average molecular weight and the molecular weight distribution index of the polymer were measured using an LC-20A type liquid phase gel permeation chromatograph in combination with an ultraviolet detector in the following examples; measuring the molecular structure of the polymer rubber by using a Bruker AVANCE400 nuclear magnetic resonance apparatus (400 Hz); measuring the glass transition temperature of the sample by using a TA 2910 DSC type differential thermal analyzer; testing the Mooney viscosity of the raw rubber and the rubber compound by using a GT-7080-S2 Mooney viscosity machine; the tensile property of the prepared material is tested and characterized by an INSTRON material testing machine, and the testing is regulated according to national standard GB/T528-1998 determination of tensile stress strain property of vulcanized rubber or thermoplastic rubber; the test specimens were tested for dynamic compression fatigue heat generation using an RH-2000 rubber compression heat generation tester according to GB/T1687-1993.
Example 1
7000mL of n-hexane and 1.5-diazobicyclo [4,3,0] -5-nonene (DBN) 1.0mL of 1.5-diazobicyclo [4,3,0] -5-nonene (DBN) were added to a 10-liter polymerization vessel under nitrogen protection, 1060g of butadiene and 300g of isoprene were then added to the polymerization vessel under nitrogen pressure, stirring was started, the polymerization solution was again warmed to 75℃under nitrogen protection of 0.35MPa, then 0.72mol/L of NBL 13.5mL was added, followed by dropwise addition of 9.5mmol of DVB hexane thin solution to the polymerization vessel for 45 minutes, at which time the temperature of the dope was raised to 95.6℃at the maximum temperature after 45 minutes of the polymerization reaction mass, and the warming rate was 0.46℃per minute. Then stirring and reacting for 20min, adding 13mL of N, N' -dimethyl imidazolinone with the concentration of 0.7mol/L into a polymerization kettle, and reacting for 15-20 min at the temperature of not higher than 90 ℃.
And then, removing the polymerized glue solution from the polymerization kettle, adding 3.5g of antioxidant 1076, uniformly mixing, condensing the glue solution by water vapor, and drying to obtain the product.
As a result, it was found that the number average molecular weight Mn=14.95×10 of the raw rubber 4 A molecular weight distribution index of 2.58; the content of 1, 2-addition units in polybutadiene units in raw rubber was 8.94%, and the content of trans-1, 4-addition units was 76.21%; the 3, 4-addition unit content in the polyisoprene unit is 8.75%, and the trans 1, 4-addition unit content is 74.86%; the Mooney viscosity ML of the raw rubber is 51.6; tg is-85.7deg.C.
Example 2
The relevant process conditions in example 1 were kept unchanged except that 0.9mL of DBN was added, the mixed monomer for the first stage consisted of 1100g of butadiene and 350g of isoprene, the butyllithium added was 12mL, the divinylbenzene for continuous dropwise addition was 10.8mmol, and the continuous dropwise addition time was 50min; and 12mL of N, N' -dimethylimidazolidinone for the second-stage active chain lithium end capping.
As a result, it was found that the number average molecular weight Mn=16.78X10 of the raw rubber 4 A molecular weight distribution index of 2.74; the content of 1, 2-addition units in polybutadiene units in raw rubber is 8.43%, and the content of trans-1, 4-addition units is 78.56%; the 3, 4-addition unit content in the polyisoprene unit is 6.42%, and the trans 1, 4-addition unit content is 81.86%; the Mooney viscosity ML of the raw rubber is 58.5; tg is-84.6 ℃.
Example 3
The relevant process conditions in example 2 were kept unchanged except that 1.2mL of DBU was added, the mixed monomer for the first stage consisted of 900g of butadiene and 500g of isoprene, the butyllithium added was 10mL, the divinylbenzene for continuous dropwise addition was 11.8mmol, and the continuous dropwise addition time was 48min. And (3) reacting 10mL of N, N' -dimethyl imidazolinone for end capping of the second active chain lithium at the temperature of 85-90 ℃ for 20min, adding 9mL of 0.7mol/L tributyl tin chloride hexane solution into a polymerization kettle, and reacting at the temperature of 80-85 ℃ for 20min.
As a result, it was found that the number average molecular weight Mn=19.24×10 of the raw rubber 4 A molecular weight distribution index of 2.86; the content of 1, 2-addition units in polybutadiene units in raw rubber is 7.46%, and the content of trans-1, 4-addition units is 78.94%; the content of 3, 4-addition units in the polyisoprene unit is 6.23%, and the content of trans-1, 4-addition units is 75.82%; the Mooney viscosity ML of the raw rubber is 62.7; tg is-83.4 ℃.
Example 4
The relevant process conditions in example 3 were kept unchanged except that 1.3mL of DBU was added, the mixed monomer for the first stage consisted of 800g of butadiene and 600g of isoprene, the initiation temperature of polymerization was 80℃and the highest temperature of polymerization was controlled to be not higher than 100℃with 9mL of butyllithium added, 12.5mmol of divinylbenzene for continuous dropwise addition, and the continuous dropwise addition time was 45 minutes; 8mL of N, N' -dimethylimidazolidinone for second-stage active chain lithium end capping and 8mL of hexane solution of tributyltin chloride.
As a result, it was found that the number average molecular weight Mn of the raw rubber was 21.6X10 4 Molecular weight distribution index d=3.12; the content of 1, 2-addition units in polybutadiene units in raw rubber is 4.23%, and the content of trans-1, 4-addition units is 86.12%; the content of 3, 4-addition units in the polyisoprene unit is 5.12%, and the content of trans 1, 4-addition units is 84.56%; the Mooney viscosity ML of the raw rubber is 66.7; tg is-81.8 ℃.
Example 5
The relevant process conditions in example 2 were kept unchanged, the mixed monomer used in the first stage consisted of 1000g butadiene and 200g isoprene, 1.4mL of DBU was added, the initiation temperature of polymerization was 80 ℃, the highest temperature of polymerization was controlled to be not higher than 100 ℃, the added butyllithium was 9mL, the divinylbenzene used was continuously added dropwise, and the continuous addition time was 50min; 9mL of tributyl stannyl chloride hexane solution for end capping of the second stage active chain lithium.
As a result, it was found that the number average molecular weight Mn=18.4X10 of the raw rubber 4 Molecular weight distribution index d=3.34; the content of 1, 2-addition units in polybutadiene units in raw rubber is 4.63%, and the content of trans-1, 4-addition units is 87.94%; the 3, 4-addition unit content in the polyisoprene unit is 4.47%, and the trans 1, 4-addition unit content is 88.21%; the Mooney viscosity ML of the raw rubber is 60.6; tg is-83.7 ℃.
Example 6
The relevant process conditions in example 5 were kept unchanged, except that the mixed monomer for the first stage consisted of 300g butadiene and 1200g isoprene, 1.2mL of DBU was added, 8.5mL of butyllithium was added, 16.0mmol of divinylbenzene was continuously added dropwise, and the continuous addition time was 50min; 8mL of tributyl stannyl chloride hexane solution for end capping of the second stage active chain lithium.
As a result, it was found that the number average molecular weight Mn=24.8X10 of the raw rubber 4 Molecular weight distribution index d=3.48; the content of 1, 2-addition units in polybutadiene units in raw rubber is 4.92%, and the content of trans-1, 4-addition units is 84.94%; the 3, 4-addition unit content in the polyisoprene unit is 5.05%, and the trans 1, 4-addition unit content is 85.36%; the Mooney viscosity ML of the raw rubber is 70.4; tg is-82.4 ℃.
Application example 1 (rubber for tire base)
Will be solidThe broad distribution polybutadiene-isoprene (containing gradient block BIR) and load-AlR prepared in example 1 3 The three samples of TBIR and BR-9000 with the Mooney viscosity of 62 prepared by catalysis are respectively matched with NR, and the rubber formula for the tire base and the preparation method are used for mixing and vulcanizing, so that the physical properties of the prepared composite material for the tire base are shown in Table 1.
Table 1 physical properties of composite materials for tire base
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Note that: the formula comprises the following components: 30 parts of BIR containing gradient blocks, 70 parts of NR, 40 parts of carbon black, 18 parts of filling operation oil, 20 parts of white carbon black, 3.0 parts of silicon-693 parts of zinc oxide, 2.0 parts of stearic acid, 1.5 parts of anti-aging agent 4010, 1.2 parts of anti-aging agent RD, 1.0 parts of accelerator NS, 1.8 parts of accelerator CZ and 3.2 parts of sulfur.
From the data in Table 1, it was found that the gradient-block-containing BIR of the present invention was used in combination with NR for TBIR and BR-9000, respectively, to obtain a rubber compound for a tire base having the same ratio of high elongation, high hardness, high rebound, low heat generation and aging resistance.
Application example 2 (rubber for tire sidewall)
BIR containing gradient block prepared in example 1 and supported titanium-AlR 3 The three samples of TBIR (trans-butyl-pentyl rubber) and BR-9000 with the Mooney viscosity of 62 prepared by catalysis are respectively matched with NR, and the tire side composite material prepared by mixing and vulcanizing according to the tire side formula and the preparation method provided by the invention has the physical properties shown in Table 1.
Table 1 physical properties of tire side composites
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Note that:
(1) TBIR Shandong Hua polymeric Polymer Material technologies Co.
(2) Example 1 and comparative formulation: NR50 parts; 50 parts of BIR containing gradient blocks; 55 parts of super wear-resistant carbon black; si-69 parts; 13 parts of environment-friendly rubber oil; 1165 20 parts of ZEOSIL; 2 parts of octyl phenolic tackifying resin; 2.0 parts of accelerator DM; 1.3 parts of promoter CZ; 2.0 parts of zinc oxide; 1.5 parts of stearic acid; 1.2 parts of anti-aging agent 4010; 1.5 parts of an anti-aging agent RD; 1.5 parts of protective wax; 1.3 parts of sulfur.
From the data in Table 1, it was found that the use of the gradient-block-containing BIR according to the present invention, in which the gradient-block-containing BIR and TBIR are used in combination with NR, can give a tire side compound having both high tensile strength and high hardness, high rebound, low heat generation and excellent aging resistance, as compared with TBIR and BR-9000, respectively.
Claims (11)
1. A wide-distribution polybutadiene-isoprene rubber is characterized in that: has the following expression;
R—B 1 I m B 2 I m-1 ……B m-1 I 2 B m I 1 D—F
wherein,
r is an initiator residue;
m is the number of micro blocks;
B 1 ……B m is m butadiene homo-blocks and is composed of B 1 To B m The chain length of the butadiene homo-polymer block of (2) is gradually decreased;
I 1 ……I m is m isoprene homo-blocks and is represented by I 1 To I m The chain length of the isoprene homopolymerization block of the (B) is gradually decreased in a gradient manner;
d is a divinylbenzene branching unit, and the average branching degree is 1-2.5;
f is a polar end capping group;
the number average molecular weight Mn=15 to 25×10 of the wide distribution polybutadiene-isoprene rubber 4 The molecular mass distribution index is 2.5-3.5;
the number ratio of 1, 2-addition units of butadiene to 3, 4-addition units of isoprene in the widely distributed polybutadiene-isoprene rubber is less than 10%, and the number ratio of trans-1, 4-addition units of polyisoprene and polybutadiene units is greater than 75%.
2. The broad distribution polybutadiene-isoprene rubber according to claim 1, characterized in that: the raw rubber mooney viscosity ml=50-70 of the wide-distribution polybutadiene-isoprene rubber.
3. The process for preparing a wide-distribution polybutadiene-isoprene rubber according to claim 1 or 2, characterized in that: adding diazonium reagent, butadiene and isoprene into an anionic polymerization solution system, heating to an initiation temperature, adding alkyl lithium into the anionic polymerization solution system to initiate polymerization reaction, and continuously and slowly adding divinylbenzene into the anionic polymerization solution system in the polymerization reaction process; and after the polymerization reaction is finished, adding a polar end-capping agent into the anionic polymerization solution system to carry out end-capping reaction, thus obtaining the polymer.
4. The method for preparing a wide-distribution polybutadiene-isoprene rubber according to claim 3, wherein:
the mass ratio of butadiene to isoprene is (20-80): 80-20;
the molar ratio of divinylbenzene to alkyllithium is (1.0-3.0): 1;
the molar ratio of the diazonium reagent to the alkyl lithium is (0.5-1.6): 1;
the divinylbenzene accounts for 0.08-0.16% of the total mass of the butadiene and the isoprene.
5. The method for preparing a wide-distribution polybutadiene-isoprene rubber according to claim 3, wherein: the diazonium reagent is at least one of 1, 5-diazobicyclo [4,3,0] -5-nonene or 1, 8-diazobicyclo [5,4,0] -7-undecene.
6. The method for preparing a wide-distribution polybutadiene-isoprene rubber according to claim 3, wherein: the initiation and polymerization reaction temperature is within the range of 50-100 ℃.
7. The method for preparing a wide-distribution polybutadiene-isoprene rubber according to claim 3, wherein: the anionic polymerization solution system comprises at least one solvent of benzene, toluene, cyclohexane and n-hexane.
8. The preparation method of the wide-distribution polybutadiene-isoprene rubber according to any one of claims 3-7, wherein the preparation method is characterized in that: the time for continuously adding the divinylbenzene into the anionic polymerization solution system is controlled within the range of 40-80 min, and the polymerization reaction is continued for 20-30 min after the divinylbenzene is added.
9. The method for preparing a wide-distribution polybutadiene-isoprene rubber according to claim 8, wherein: the divinylbenzene is added as a dilute solution after dilution with a solvent.
10. The method for preparing a wide-distribution polybutadiene-isoprene rubber according to claim 3, wherein: the polar end-capping agent comprises at least one element of tin, nitrogen, oxygen and silicon, and comprises at least one functional group capable of reacting with active lithium in halogen, ketone, acid, amine or ester.
11. The method for producing a wide-distribution polybutadiene-isoprene rubber according to claim 3 or 10, characterized in that: the temperature of the end capping reaction is 50-90 ℃ and the time is 15-20 min.
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