CN112210053A - Polybutadiene-isoprene rubber containing both micro-block and long-chain block and preparation method thereof - Google Patents
Polybutadiene-isoprene rubber containing both micro-block and long-chain block and preparation method thereof Download PDFInfo
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- CN112210053A CN112210053A CN201910613149.XA CN201910613149A CN112210053A CN 112210053 A CN112210053 A CN 112210053A CN 201910613149 A CN201910613149 A CN 201910613149A CN 112210053 A CN112210053 A CN 112210053A
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- isoprene
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- 229920003049 isoprene rubber Polymers 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 129
- 229920001971 elastomer Polymers 0.000 claims abstract description 125
- 239000005060 rubber Substances 0.000 claims abstract description 123
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 87
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000000178 monomer Substances 0.000 claims abstract description 52
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 35
- 238000009826 distribution Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000011925 1,2-addition Methods 0.000 claims abstract description 15
- -1 alkyl lithium Chemical compound 0.000 claims abstract description 12
- 230000000977 initiatory effect Effects 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 23
- 229920001195 polyisoprene Polymers 0.000 claims description 18
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 15
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 238000007334 copolymerization reaction Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 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
- 239000012190 activator Substances 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 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
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 244000043261 Hevea brasiliensis Species 0.000 abstract description 24
- 229920001577 copolymer Polymers 0.000 abstract description 24
- 229920003052 natural elastomer Polymers 0.000 abstract description 22
- 229920001194 natural rubber Polymers 0.000 abstract description 22
- 230000003712 anti-aging effect Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000005336 cracking Methods 0.000 abstract description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 31
- 239000005062 Polybutadiene Substances 0.000 description 29
- 239000002131 composite material Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 239000006229 carbon black Substances 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- 239000004636 vulcanized rubber Substances 0.000 description 12
- 230000032683 aging Effects 0.000 description 11
- 230000020169 heat generation Effects 0.000 description 10
- 229920006978 SSBR Polymers 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 229920002857 polybutadiene Polymers 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000004073 vulcanization Methods 0.000 description 8
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000945 filler Substances 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
- 239000003921 oil Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 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 3
- 238000013329 compounding Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000003825 pressing Methods 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
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N trimethylsilyl-trifluoromethansulfonate Natural products C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 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
- 239000004970 Chain extender Substances 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 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
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 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
- YSZKOFNTXPLTCU-UHFFFAOYSA-N barium lithium Chemical compound [Li].[Ba] YSZKOFNTXPLTCU-UHFFFAOYSA-N 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 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
- 125000004433 nitrogen atom Chemical group N* 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
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 230000001012 protector Effects 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
- 238000007789 sealing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 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
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
- 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
-
- 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
-
- 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
-
- 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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- 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)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses polybutadiene-isoprene rubber containing both micro-blocks and long-chain blocks and a preparation method thereof. Butadiene, isoprene and divinylbenzene are taken as mixed monomers, alkyl lithium is taken as a catalyst, and the polybutadiene-isoprene rubber which has wide molecular mass distribution, high melt elasticity and good processing performance and contains micro-blocks and long-chain blocks is obtained through the processes of slow initiation, slow growth, polar end capping and the like, wherein the number proportion of 1, 2-addition units and 3, 4-addition units of isoprene in the molecules of the copolymer rubber is less than 10%, and the number proportion of trans-addition units of isoprene units and butadiene units is higher than 80%, so that the copolymer rubber is suitable for rubber for tire treads, tire sidewalls, inner liners and belt layers, and particularly shows excellent compatibility, anti-cracking performance and anti-aging performance after being compounded with natural rubber.
Description
Technical Field
The invention relates to a polybutadiene-isoprene rubber, in particular to a polybutadiene-isoprene rubber which is synthesized by taking butadiene and isoprene as monomers and divinylbenzene as a branching agent through lithium-based catalysis and has the characteristics of simultaneously containing polyisoprene micro-blocks, long-chain blocks, trans-1, 4 structures, wide distribution and the like, is particularly suitable for rubber for tire treads, tire sidewalls, inner liners and belt layers, and belongs to the field of tire rubber.
Background
BR-9000 in the prior art is a common tire rubber material, but has the Tg of-100 ℃, the polymer molecular chain height is regular, the rubber material has strong crystallization tendency, becomes hard at the temperature of-35 ℃, and is easy to lose elasticity, and rubber for parts of a belt layer, a side wall and the like of the tire is usually combined by Natural Rubber (NR) and BR, so that the rubber material and the BR are incompatible, the prepared tire is easy to crack, and the service life of the tire is influenced.
The trans-butadiene-isoprene rubber (TBIR) has lower crystalline melting point and crystallinity than TIR, has obviously improved processing performance, is a novel elastomer material, and can be widely used for tire treads, sidewalls, inner liners and belted layers.
The catalytic system for preparing polybutadiene-isoprene (BIR) rubber is transition metal, lithium system and rare earth, etc. The TBIR prepared by the Ti-Mg coordination catalytic system has low compression heat generation, fatigue resistance, tear resistance, wear resistance and low noise, has outstanding crude rubber strength, is an ideal rubber material for high-performance tires, and has the defect of monomer conversionThe rate is less than 70%, and the self-adhesiveness of the raw rubber is low; in the conventional lithium-based catalyst for synthesizing BIR, the 1, 4-addition content of butadiene and isoprene is increased and the 1.2-and 3, 4-addition content of the butadiene and isoprene is reduced along with the increase of the polymerization temperature, but the molecular mass distribution of the polymer is too narrow, the green strength is low, the cold flow is large, the processability is poor and the like. For example, U.S. Pat. No. 5,54, 05927 describes the copolymerization of isoprene-butadiene synthesized by organolithium/barium salt catalysis, the melting point of the copolymer decreases with the increase of the isoprene content in the monomer, and the copolymer can be stretched and crystallized, thereby increasing the strength and viscosity of the raw rubber, and the rubber is suitable for the tread rubber of the tire. Furthermore, British patent GB2029426 and U.S. Pat. No. 4,973,89 describe random or block copolymers obtained by copolymerization of butadiene and isoprene using barium salt-lithium tributyl magnesium/trialkylaluminum as a catalyst, which have a Mooney viscosity of 59 and a molecular weight distribution D of 1.46, are excellent in processability and crude rubber tackiness, and can be used in combination with natural rubber NR. European patent EP629640 reports that rare earth is adopted to catalyze butadiene and isoprene to carry out copolymerization, the cis content of two monomers can reach more than 96 percent, the two monomers are ideal random copolymerization, and r in the system isbd＝1.09，rIpThe ratio of the two rates of polymerization was close to 1 at 1.32, and the Tg of the polymer was-73 ℃. Chinese patent CN105985487A discloses a butadiene-isoprene copolymer rubber with both ends of a macromolecular chain functionalized and modified, which adopts a functionalized 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, the butadiene-isoprene copolymer rubber can effectively participate in the elastic recovery of the whole crosslinking network, the energy loss in periodic deformation is reduced, and the heat generation and rolling resistance are improved, but the functionalized initiator is unstable and easy to inactivate, and has the defects of difficult preparation and the like. Chinese patent CN103387641A introduces a trans-1, 4-structure butadiene-isoprene copolymer rubber and a preparation method thereof, and concretely adopts MgCl2The butadiene-isoprene copolymer rubber with a trans-1, 4-structure of more than 90% is synthesized by catalyzing butadiene and isoprene to copolymerize by a Ziegler-Natta catalyst system consisting of supported titanium and an organic aluminum compound, and the copolymer rubber comprises 20-99.5% of isoprene units and 0.5-80% of butadiene units in molar fractionAnd (4) meta-composition. The preparation method of the trans-copolymer rubber comprises the steps of fixing the feed ratio of butadiene to isoprene, and catalyzing butadiene and isoprene to be copolymerized at 0-90 ℃ to synthesize the trans-copolymer rubber composed in a gradient manner. Chinese patent CN106699966A provides a butadiene-isoprene copolymer rubber and a preparation method thereof, and specifically discloses that the molecular chain of the copolymer rubber is composed of a butadiene homopolymerization section and a butadiene-isoprene random copolymerization section, wherein the number average molecular weight of the butadiene homopolymerization section is 5-30 ten thousand, the content of cis-form 1, 4-structures in the butadiene homopolymerization section is not less than 97 mol%, and the number average molecular weight of the butadiene-isoprene random copolymerization section is 5-50 ten thousand. The butadiene-isoprene copolymer rubber provided has excellent mechanical strength and flex crack resistance.
The variation in conversion rates H was investigated in the text "Effect of conversion on the Properties of high trans-1, 4-butadiene-isoprene rubber" petrochemical, 03 2010)2Adjusting to TiCl4/MgCl2The 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 viscosity is similar, the green strength, the elongation at break and the permanent tensile deformation of the TBIR rubber are increased along with the increase of the conversion rate, and the abrasion and the rebound resilience of the TBIR vulcanized rubber Akron are increased along with the increase of the conversion rate. However, as monomer conversion increases, wet skid resistance of the TBIR vulcanizate decreases and heat generation increases. When the initial feeding ratio n (Bd) n (ip) is 0.25, the conversion rate is controlled at 55-65%, and the comprehensive performance of the TBIR vulcanized rubber is optimal. TBIR is applied to tire bead protection rubber in the text of structural characterization of high trans-1, 4-butadiene-isoprene copolymer rubber and application research thereof in the bead protection rubber of car tires, published by the high molecular report, 2015.12 (12), so that the crystallinity, the green strength and the hardness of rubber compound can be increased, and the vulcanization speed is accelerated; other properties of the TBIR-containing blended vulcanizate remain unchanged and compression is performedThe temperature rise is obviously reduced, and the abrasion resistance and the aging resistance are obviously improved; the compatibility of TBIR with NR is superior to BR. The result shows that after NR is used together with TBIR, the carbon black in vulcanized rubber has better dispersibility, about 20 parts of TBIR is applied to the bead protector of the radial tire of a passenger car, other mechanical properties are kept at a higher level, meanwhile, the wear resistance, the flex resistance and the aging resistance are obviously improved, and the compression temperature rise is obviously reduced. The application of a new generation of synthetic rubber-trans-1, 4-butadiene-isoprene copolymer rubber (TBIR) in high-performance passenger car tire tread rubber (solution-polymerized styrene-butadiene rubber/butadiene rubber, SSBR/BR) and the structure and performance of the SSBR/BR/TBIR blended rubber are described in the' high molecular report of structure and performance of a trans-1, 4-butadiene-isoprene copolymer rubber modified high-performance passenger car tire tread rubber, 2018, 03). The results show that: TBIR exhibits higher green strength, modulus and toughness relative to amorphous SSBR and BR due to some crystallinity. 10-20 parts of TBIR and SSBR/BR are modified simultaneously, 30 parts of carbon black and 45 parts of white carbon black are added simultaneously, the Green strength and the stress at definite elongation of the SSBR/BR/TBIR rubber compound are improved, the scorching time (tc10) and the normal vulcanization time (tc90) are basically kept unchanged, the vulcanized rubber of the SSBR/BR/TBIR rubber compound has excellent 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-slip 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 μm. The high green rubber strength and modulus of the crystallizable TBIR can obviously inhibit the aggregation of the filler in the rubber compound, improve the dispersibility of the filler in the vulcanized rubber, and finally contribute to the excellent tensile fatigue resistance, high wear resistance, wet skid resistance, compressive strength, constant tensile modulus and other properties of the SSBR/BR/TBIR vulcanized rubber, wherein the TBIR is an ideal novel synthetic rubber applied to the high-performance car tire tread rubber. In addition, the effect of the relative molecular mass and its distribution on the properties of the high trans-1, 4-butadiene-isoprene copolymer rubber, rubber industry, 12 2010) was studied in the study of the relative molecular mass (Mooney viscosity) and its distribution on the trans-1, 4-butadiene-isoprene copolymerInfluence of Rubber (TBIR) Properties. The results show that: the plastication and mixing performance of the TBIR are gradually improved along with the reduction of the Mooney viscosity, the mixing difficulty of the TBIR with the Mooney viscosity of more than 60 is increased, and the processing performance is poor; the comprehensive physical property of the TBIR is improved along with the increase of the Mooney viscosity, but the improvement effect of the physical property and the dynamic property of the rubber is not obvious after the Mooney viscosity is more than 55, and the comprehensive property of the TBIR rubber is optimal when the Mooney viscosity is 50-60. The tensile property, abrasion resistance and heat generation property of the TBIR crude rubber and vulcanized rubber which are bimodal relative to the molecular mass distribution are better; the yield resistance of the TBIR vulcanized rubber with a single peak relative to the molecular mass distribution can be greatly improved.
The trans-1, 4-TBIR destroys the structural regularity of TPI main chain, the crystallinity is obviously reduced, the radial tire belt ply is positioned at the base of the tire and plays a role of hoop tightening the tire body to relax the impact, the radial tire belt ply is a main stress component of the tire, the rubber material has the characteristics of good adhesion with steel wires, ageing resistance, low rolling resistance and the like, and the traditional belt ply formula adopts NR as a base body.
Goodyear reports high-performance tire crown rubber containing TBIR, the digging and winding fatigue resistance of the tire crown rubber is respectively 10-100 times of NR/BR, and the tire crown rubber is particularly suitable for digging and winding tire side and bead parts with high fatigue.
The literature (He Aihua, Polym. Sci.2003,89(7):1800-(Bd)(iii) an isoprene polymerization rate r of 5.7(IP)0.17. In addition, research of Qingdao science and technology university shows that the length of an IP chain link in the TBIR is increased along with the increase of the conversion rate, and when the conversion rate is 55-65%, the TBIR is mainly long-chain IP. The raw rubber has high strength, elongation at break and deformation, and the comprehensive performance is optimal. The TBIR synthesis technology is produced by rubber and plastic new materials GmbH of Dongyngguri in Shandong.
The application of high-ethylene solution polymerized styrene-butadiene rubber in high-performance tread rubber, Elastomers 2013, 23 (3): 53-58, introduced in Zhang Jian et al, discloses that the content of butadiene unit 1, 2-addition product, cis-1, 4-addition product and trans-T-1, 4-addition product in lithium polymerized styrene-butadiene rubber is 62-68%, 6-8% and 26-32%. Namely, the trans-1, 4-addition product content of the polymer obtained by the traditional lithium-catalyzed butadiene or isoprene polymerization under the regulation action of a high-efficiency activator is not higher than 40 percent.
In conclusion, the monomer conversion rate of the high trans-1, 4-butadiene-isoprene rubber (TBIR) catalyzed and synthesized 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, and the defects are that the requirements of the development of the high-performance green tire at present are not met. The studies on trans-polybutadiene-isoprene rubber (BIR) having a block distribution and a high content, which is prepared by lithium-based polymerization, are not common.
Disclosure of Invention
In order to overcome the problems that the existing composite material prepared by compounding high cis BR and NR has poor performance, or BR synthesized by lithium catalysis has too narrow molecular weight distribution, poor processing performance, low T-1,4 content and easy crystallization, the existing TBIR has poor processing performance due to high viscosity, and the like, the first aim of the invention is to provide a polybutadiene-isoprene rubber (BIR) which has high branching degree, wide molecular mass distribution and contains both polyisoprene micro-block and polyisoprene long chain block, and in the rubber, the addition units of 1, 2-addition units and 3, 4-content of isoprene block are both less than 10%, the addition contents of cis (c-1,4) addition units of isoprene unit and butadiene unit are both less than 8%, and the contents of trans T-1,4 addition products are both higher than 80%, thus improving the strength and melt elasticity of polymer crude rubber, the crystallinity of the crystal is reduced; the rubber and the natural rubber are used for a radial tire tread, a tire side, an inner liner and a belted layer, have good compatibility, strengthen the ageing resistance and the cracking resistance of a vulcanized composite material, improve the stress and the buffer impact resistance of a tire body and reduce the rolling resistance of the tire; particularly, the composite sizing material has the characteristics of good adhesion with steel wires, aging resistance, digging (winding) fatigue resistance and the like, and can replace BR in the traditional formula or the existing TBIR (the defects of poor compatibility, easy aging and cracking of a matrix manufactured by compounding BR and NR).
The second purpose of the invention is to provide a method for preparing polybutadiene-isoprene rubber with high branching, isoprene-containing micro-block, long chain homopolymerized block and wide distribution trans-1, 4 structure by taking butadiene and isoprene as monomer raw materials and divinylbenzene as a chain extender through lithium system catalysis, the method utilizes the characteristics of n-butyl lithium slow initiation monomer, slow growth of copolymer chain and fast end capping of polar functional compound, the synthesized copolymer rubber has wide molecular mass distribution, high melt elasticity and good processing performance, the content of trans-T-1, 4 additive is higher than 80 percent, the copolymer rubber is suitable for tire treads, tire sidewalls, inner liners and belt layers, particularly has excellent compatibility, anti-cracking and anti-aging performance with natural rubber complex, the synthesis method has simple and mature operation and low cost, is beneficial to industrial production.
In order to achieve the above technical object, the present invention provides a polybutadiene-isoprene rubber containing both micro-blocks and long-chain blocks, which has the following expression:
R—BID—Im—F
wherein,
r is an initiator residue;
BID is a random copolymerization block of butadiene, isoprene and divinylbenzene, the random copolymerization block comprises a butadiene homopolymerization micro-block with the polymerization degree of more than or equal to 1 and an isoprene homopolymerization micro-block with the polymerization degree of more than or equal to 1, and the chain lengths of the butadiene homopolymerization micro-block and the isoprene homopolymerization micro-block are in gradient distribution;
d is a divinylbenzene branching unit, and the average branching degree is 1-2.5;
Imis a long-chain isoprene homopolymer block;
f is a polar end capping group;
the polybutadiene-isoprene rubber containing both the micro block and the long chain block has a number average molecular weight Mn of 12-25 × 104The molecular mass distribution index is 1.75-2.20.
Preferably, the polybutadiene-isoprene rubber containing both the micro-block and the long-chain block contains a polyisoprene block with the number average molecular weight of 4000-20000.
In a preferred embodiment, the polybutadiene-isoprene rubber containing both micro-blocks and long-chain blocks has a ratio of the number of 1, 2-addition units of butadiene to the number of 3, 4-addition units of isoprene of less than 10%, and a ratio of the number of trans-addition units of isoprene units to the number of trans-addition units of butadiene of more than 80%.
Preferably, the raw rubber Mooney viscosity ML of the polybutadiene-isoprene rubber containing both the micro-block and the long-chain block is 50-70.
In the polybutadiene-isoprene rubber (F-TBIR) containing both the micro block and the long chain block, the branching degree of D can be 0, 1,2, 3 and … randomly, and the average n is 1-2.5.
R is n-butyl or n-butyl lithium initiation residue.
The invention provides polybutadiene-isoprene rubber containing both micro-block and long-chain block, wherein the chain length of butadiene homopolymerization micro-block presents gradient distribution, and the micro-block polymerization degree with B larger than I is generated at the early stage of polymerization reaction; and in the later period of the polymerization reaction, the polymerization degree of the micro-block with I being larger than that of B. Namely, the partial chain link of the butadiene and isoprene copolymer molecular chain in the BID block has the following structure:
～Ba-Ix-Bb-Iy-Bc-Iz～
wherein a > b > c, x < y < z. The polymerization degrees a, b, c, …, x, y, z, … and the like in each branched long chain molecule are different, but the homopolymerization polymerization degree m of the second-stage isoprene is a constant value, and different total polymerization degree values determine the molecular mass of the branched chain segment, and simultaneously show that the polymer has different molecular mass distributions and distribution fractions.
The invention also provides a preparation method of the polybutadiene-isoprene rubber containing both the micro-block and the long-chain block, which comprises the steps of continuously and slowly adding the mixed monomer of butadiene, isoprene and divinylbenzene and alkyl lithium into an anionic polymerization solution system preheated to the initiation temperature for polymerization reaction; after the mixed monomer and the alkyl lithium are added, adding an isoprene monomer into an anion polymerization solution system for chain extension reaction; and after the chain extension reaction is finished, adding a polar end capping agent into an anionic polymerization solution system to carry out end capping reaction, thus obtaining the modified polyurethane.
Preferably, the ratio of the mass of the butadiene monomer to the total mass of the isoprene monomer in the polymerization reaction and the chain extension reaction is (20-80): (80-20). By fixing the feed ratio of butadiene, isoprene and divinylbenzene, mixed monomers are initiated by butyl lithium in an organic solution, the polymerization reaction has the characteristics of continuous initiation, chain extension and irregular branching of long-short chains, the content of 1, 2-addition units and 3, 4-addition units in molecular chain extension is low, the content of trans-1, 4-addition units is high, and a polyisoprene micro-block and a long-chain homopolymerization block are also arranged in a copolymer molecular chain.
In a preferred scheme, the mass percentage content of the divinylbenzene in the mixed monomer is 0.10-0.2%. The divinyl benzene in the polybutadiene-isoprene rubber containing both the micro block and the long chain block is doped into a molecular chain through random copolymerization, some molecular chain segments do not contain a divinyl benzene unit, and some molecular chain segments contain a plurality of branching units.
Preferably, the mass ratio of the isoprene monomer in the polymerization reaction to the isoprene monomer in the chain extension reaction is (70-90%): 10-30%. According to the invention, isoprene is added in batches, so that the copolymer molecule not only contains a micro-block polyisoprene unit, but also contains a longer molecular chain segment polyisoprene homopolymerization unit, namely the prepared raw rubber and natural rubber have excellent compatibility after compound vulcanization, and the tire prepared by using the rubber can improve the ageing resistance and the crack resistance of the composite material.
In a preferable scheme, the molecular ratio of the divinyl benzene to the alkyl lithium is (1.0-2.5): 1. The alkyllithium is preferably n-butyllithium.
In a preferable scheme, the anionic polymerization solution system comprises an anisole activator, and the concentration of the anisole activator in the anionic polymerization solution system is 5-10 mg/kg.
In a preferred embodiment, the anionic polymerization solution system comprises at least one solvent selected from benzene, toluene, cyclohexane and n-hexane. The preferred solvent is n-hexane.
According to the preferable scheme, the mixed monomer of butadiene, isoprene and divinylbenzene and alkyl lithium are continuously added into an anionic polymerization solution system preheated to 40-90 ℃ for polymerization reaction, and the continuous adding time of the mixed monomer and the alkyl lithium is controlled within the range of 40-120 min. The preferable polymerization temperature is 70-90 ℃, and the higher polymerization temperature is beneficial to improving the rate of trans-1, 4 addition and reducing the ratio of 1, 2-addition and 1, 3-addition. The preferable feeding time of continuously feeding the mixed monomer and the lithium alkyl into the polymerization kettle is 60-90 min. The content of 1, 2-addition product of butadiene segment and 3, 4-addition product of isoprene segment in polymer molecule can be controlled to be less than 10%, in which the cis (c-1,4) addition content of polyisoprene and polybutadiene units is less than 8%, and the trans T-1,4 addition content is more than 80%.
In the preferable scheme, the temperature of the chain extension reaction is 80-90 ℃ and the time is 20-25 min.
In a preferred embodiment, the polar capping agent comprises at least one element selected from tin, nitrogen, oxygen, and silicon, and comprises at least one functional group selected from halogen, ketone, acid, amine, and ester, which is capable of reacting with active lithium. The polar capping agent of the present invention may be selected from polar compounds commonly found in the art. Preferably at least one or more compounds containing atoms such as tin, nitrogen, oxygen, silicon and the like, halogen or ketone or acid or ester and the like and capable of being added or condensed with active lithium, such as tributyl tin chloride, N' -dimethyl imidazolidinone, trimethyl monochlorosilane and the like. Most preferred is one of N, N '-dimethylimidazolidinone and tributyltin chloride, or the carbonyl group in the N, N' -dimethylimidazolidinone molecule is preferably added with active chain lithium to form [ -O ]-Li+]Then tributyltin chloride and-O are used-Li+Condensation and sealing are carried out. The addition amount of the end capping reagent is preferably equal molar amount of active lithium, wherein the preferable closed reaction time is 15-20min, and the reaction temperature is 50-85 ℃.
In the preferable scheme, the temperature of the end-capping reaction is 50-85 ℃, and the time is 15-20 min.
The polybutadiene-isoprene rubber containing both micro-blocks and long-chain blocks is synthesized by adopting an anionic polymerization method, n-butyl lithium is taken as an initiator, a trace amount of divinylbenzene is taken as a molecular chain branching and molecular mass distribution regulator, a polar compound is taken as an end capping agent, hexane is taken as a solvent, a mixture of butadiene, isoprene and a trace amount of divinylbenzene is slowly initiated, the molecular chain of copolymerization is slowly increased, and finally the copolymerization glue solution containing active chain terminal lithium is quickly sealed by a polar group, so that the polybutadiene-isoprene rubber (BIR) containing the isoprene micro-blocks and long-chain blocks, which has low vinyl and 3, 4-addition unit content, high trans-1, 4-addition unit content, wide molecular mass distribution, a long-chain branching structure and high isoprene homopolymer and long-chain blocks is obtained.
The specific synthetic method of the polybutadiene-isoprene rubber containing both the micro block and the long chain block comprises the following steps:
1) first-stage polymerization: adding a certain amount of solvent into a polymerization kettle, metering a certain amount of butadiene, isoprene accounting for 70-90% of the total amount and a small amount of divinylbenzene in a prepared monomer metering tank, and uniformly mixing; starting stirring, heating the polymerization kettle to an initiation temperature by using hot water, continuously adding a set amount of butyl lithium and simultaneously continuously adding a mixed monomer, wherein the continuous feeding time of the butyl lithium and the mixed monomer is 60-90 min.
2) Second-stage polymerization: after the first-stage polymerization mixed monomer is added, adding 10-30% of the total amount of the set isoprene into the polymerization kettle once again for chain extension reaction, and polymerizing for 20-25 min to form polymer with active lithium containing homopolymerized polyisoprene at the tail end of a molecular chain;
3) end capping reaction: adding a certain amount of polar compound which can be condensed with the polyisoprene active lithium at the tail end of the polymer molecular chain into the polymerization kettle to carry out end capping reaction for 15-20 min;
4) and (3) coagulation and drying: and then removing the polymerized glue solution from the polymerization kettle, adding necessary antioxidant, uniformly mixing, condensing the glue solution by using water vapor, and drying to obtain the F-TBIR raw glue.
The polybutadiene-isoprene rubber containing the micro-block and the long-chain block simultaneously can be compounded with NR to be used for tire tread rubber, tire side rubber, inner liner rubber or belted layer rubber, and shows excellent performance.
The formula of the rubber for the base of the tire tread comprises the following components in parts by mass: the rubber softening agent comprises, by weight, 50-80 parts of NR, 20-50 parts of polybutadiene-isoprene rubber containing both micro blocks and long chain blocks, 30-40 parts of carbon black, 15-25 parts of rubber softening oil, 10-20 parts of white carbon black, 2.0-3.0 parts of a silane coupling agent, 3.0-4.0 parts of zinc oxide, 1.5-2.0 parts of stearic acid, 2.0-3.0 parts of an anti-aging agent, 2.0-4.0 parts of an accelerator and 3.0-3.4 parts of sulfur.
The tire side wall rubber compound formula comprises the following components in parts by mass: 30-60 parts of NR30, 30-60 parts of polybutadiene-isoprene rubber containing both micro blocks and long chain blocks, 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 formula, the adopted auxiliary agents and auxiliary materials are conventional in the field, and silane coupling agents such as Si-69 and/or silicon-75 and the like. Rubber softening oil such as TDAE, NAP-10 and A1220 obtained by hydrorefining heavy aromatic oil, etc. White carbon black such as ZEOSIL 1165. Accelerators such as accelerator NS and accelerator CZ. The tackifying resin is octyl phenolic tackifying resin.
The preparation method of the polybutadiene-isoprene rubber containing the micro-block and the long-chain block simultaneously used for the radial tire rubber material comprises the following specific steps:
firstly, adding the raw materials except sulfur into an internal mixer together for mixing, heating the mixed rubber under the shearing and friction action of a rotor of the internal mixer, raising the temperature of the mixed rubber material to 130-150 ℃, mixing for 90s, and then discharging the composite rubber mixture to form the master batch. Then putting the master batch on an open mill at 50-60 ℃, adding sulfur for mixing, cutting the left and right sides at 3/4 positions for three times respectively with an interval of 15s, adjusting the roller spacing to 0.8mm, passing through each end longitudinally for six times alternately, pressing the rubber material into a rubber sheet with the thickness of about 2.2mm, and then preparing a sample for vulcanization; the vulcanization of the rubber compound at the base part 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 (4) analyzing the physical properties of the molded vulcanized rubber.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the existing composite material prepared by compounding high cis BR and NR has poor performance, or BR synthesized by lithium catalysis has narrow molecular weight distribution, poor processability, low content of T-1,4 addition units, easy crystallization, and low monomer conversion rate or poor raw rubber processability with high viscosity in the existing TBIR synthesis. Compared with the prior art, the polybutadiene-isoprene rubber containing both the micro block and the long chain block, which is prepared by the lithium polymerization method, has the characteristics that the monomers can be completely converted, the trans-1, 4 structure content in raw rubber molecules is high, the 1, 2-addition and 3, 4-addition unit contents are low, the raw rubber molecules have long chain branching and wide distribution, the melt elasticity is large, the raw rubber strength is high, the viscosity and the elasticity are balanced, the processability is good, and the like; in addition, a group consisting of nitrogen atoms or/and tin atoms with larger polarity is introduced into the tail end of a polymer raw rubber molecular chain, the tail end blocking rate is higher than 50%, a composite material consisting of raw rubber and other rubber seeds is mixed with carbon black to be easily dispersed, the Payne effect of the vulcanized tread rubber of the composite material is reduced, meanwhile, the length and the concentration of an inert unit from a final cross-linking point of vulcanized network macromolecules to the tail end are shortened by a polar functional group, the effective elastic recovery of the macromolecules is increased, so that the energy generated in periodic deformation is easily converted into stored energy, and the heat generation and the hysteresis loss of the tire are reduced.
The polybutadiene-isoprene rubber containing both the micro block and the long chain block can be used for tire treads, tread bases, tire sidewalls, inner liners, belted layers and the like; particularly, the rubber is used as a belted layer of the tire together with natural rubber NR, has good compatibility, can replace BR in the formula of the traditional belted layer or the existing TBIR, strengthens the ageing resistance and the cracking resistance of a vulcanized composite material, improves the stress and the buffer impact resistance of a tire body, and reduces the rolling resistance of the tire; the composite rubber material composed of polybutadiene-isoprene rubber containing both micro-blocks and long-chain blocks and NR prepared by the invention has the characteristics of good adhesion with steel wires, ageing resistance, digging and winding fatigue resistance and the like, and is an important raw material of a high-performance green tire.
The reaction in the preparation of the polybutadiene-isoprene rubber containing both the micro-block and the long-chain block belongs to homogeneous reaction, the preparation is simple, the existing mature process can be utilized for synthesis, the reaction is easy to control and easy to industrialize, the production cost is lower than that of TBIR prepared by a coordination polymerization system, and no extra monomer which is not converted in the preparation of the TBIR needs to be recovered.
Detailed Description
The present invention is illustrated by the following examples, which are not intended to limit the scope or practice of the invention.
In the following examples, LC-20A type liquid gel permeation chromatograph and ultraviolet detector were used to determine the number average molecular weight and molecular weight distribution index of the polymer; the molecular structure of the polymer raw rubber is measured by a Bruker AVANCE400 nuclear magnetic resonance instrument (400 Hz); measuring the glass transition temperature of the sample by using a TA 2910DSC type differential thermal analyzer; mooney viscosities of the raw rubber and the compound rubber are measured by adopting a GT-7080-S2 model Mooney viscosity machine; testing and representing the tensile property of the prepared material by adopting an INSTRON material testing machine, and testing according to the provisions of the national standard GB/T528-; the samples were tested for dynamic compression fatigue heat generation according to GB/T1687. sup. 1993 using a RH-2000 type rubber compression heat generation tester.
Example 1
Adding 7000mL of n-hexane into a 10-liter polymerization kettle under the protection of nitrogen, starting stirring, then adding 0.05mL of 99.0% by weight of anisole, and then heating the polymerization solution to 70 ℃; at the moment, continuously pressing a pre-selected mixed monomer consisting of butadiene, isoprene and divinylbenzene into a polymerization kettle by using nitrogen gas, wherein the mixed monomer consists of 1055g of butadiene, 305g of isoprene and 1.5mL of divinylbenzene, continuously adding 0.70mol/L of NBL12mL from a sight glass of the polymerization kettle, simultaneously and continuously adding the monomer and the NBL into the polymerization kettle for polymerization for 60min, carrying out the polymerization reaction under an adiabatic condition, when the monomer and the NBL are completely added, the polymerization temperature reaches 85-90 ℃, at the moment, adding 50mL of isoprene for second-stage molecular chain extension for one time, reacting for 20min at the temperature of the polymerization kettle below 90 ℃, adding 0.7mol/L of N, N' -dimethyl imidazolidinone into the polymerization kettle for 12mL, and reacting for 15-20 min.
Then, the polymerization glue solution is removed from the polymerization kettle, 3.5g of antioxidant 1076 is added and mixed evenly, and the glue solution is condensed by water vapor and dried to obtain the product
As a result, the number average molecular weight Mn of the raw rubber was 16.6X 104The molecular weight distribution index D is 1.78; the 1, 2-addition unit content in the polybutadiene units in the raw rubber was 8.63% (wherein, the trans 1, 4-addition unit and cis 1, 4-addition unit contents were 78.96% and 12.42%, respectively); the polyisoprene rubber has a 3, 4-addition unit content of 5.36% (wherein, the trans-1, 4-addition unit content and the cis-1, 4-addition unit content are 86.42% and 8.22%, respectively; the Mooney viscosity ML of the raw rubber is 66.3; and the glass transition temperature Tg is-82.4 ℃.
Example 2
The relevant process conditions in example 1 were kept unchanged except that 0.08mL of anisole was added, 16mL of butyllithium was added, the monomer mixture and NBL continued feeding time was 70min, the amount of isoprene added in the second stage was 80mL, and 15mL of N, N' -dimethylimidazolidinone for active chain lithium capping was added, the monomer mixture for the first stage consisted of 1055g of butadiene and 305g of isoprene, and 1.8mL of divinylbenzene.
As a result, the number average molecular weight Mn of the raw rubber was found to be 12.6X 104The molecular weight distribution index D is 1.83; the 1, 2-addition unit content in the polybutadiene unit in the raw rubber is 7.87 percent, and the trans-1, 4-addition unit content in the raw rubber is 81.34 percent; the content of 3, 4-addition units in the polyisoprene units was 5.64%, and the content of trans 1, 4-addition units was 87.21%; the Mooney viscosity ML of the raw rubber is 50.6; tg was-78.8 ℃.
Example 3
The relevant process conditions in example 1 were kept constant except that 0.10mL of anisole was added, 14mL of butyllithium was added, the monomer mixture and NBL continued for 80min, the amount of isoprene added for the second stage was 100mL, and 14mL of a 0.71mol/L hexane solution of tributyltin chloride for active chain lithium capping was added, the monomer mixture for the first stage consisted of 800g of butadiene and 533g of isoprene and 2.2mL of divinylbenzene.
As a result, the number average molecular weight Mn of the raw rubber was 14.2X 104The molecular weight distribution index D is 1.88; the 1, 2-addition unit content in the polybutadiene unit in the raw rubber is 8.54 percent, and the trans-1, 4-addition unit content in the raw rubber is 82.65 percent; the content of 3, 4-addition units in the polyisoprene units is 7.48 percent, and the content of trans-1, 4-addition units in the polyisoprene units is 85.94 percent; the Mooney viscosity ML of the raw rubber is 56.8; tg was-81.4 ℃.
Example 4
Keeping the relevant process conditions in example 1 unchanged, wherein the mixed monomer used in the first stage consists of 800g of butadiene, 340g of isoprene and 2.8mL of divinylbenzene, the added butyl lithium is 10mL, the continuous feeding time of the mixed monomer and NBL is 90min, the adding amount of the second stage isoprene is 150mL, the active chain lithium is blocked, 10mLN, N' -dimethyl imidazolidinone is used for blocking addition reaction at 75-85 ℃ for 20min, and then 10mL of hexane solution of tributyltin chloride is added for terminal condensation reaction for 20 min.
As a result, the number average molecular weight Mn of the raw rubber was found to be 17.7X 104The molecular weight distribution index D is 2.16; the 1, 2-addition unit content in the polybutadiene unit in the raw rubber is 7.45 percent, and the trans-1, 4-addition unit content in the raw rubber is 83.72 percent; the content of 3, 4-addition units in the polyisoprene units was 6.94%, and the content of trans 1, 4-addition units was 85.86%; the Mooney viscosity ML of the raw rubber is 65.8; tg was-79.3 ℃.
Example 5
The relevant process conditions in example 4 were kept constant, the mixed monomer used in the first stage consisted of 1000g of butadiene and 180g of isoprene and 2.3mL of divinylbenzene, 8mL of butyllithium was added, the time for continuous addition of the mixed monomer and NBL was 90min, the polymerization initiation temperature was 80 ℃, the polymerization maximum temperature was controlled to be not higher than 90 ℃, the amount of isoprene used in the second stage was 100mL, and 8mL of a hexane solution of 8mL of N, N' -dimethylimidazolidinone and tributyltin chloride was used for active chain lithium capping.
As a result, the number average molecular weight Mn of the raw rubber was found to be 22.4X 104The molecular weight distribution index D is 2.08; the 1, 2-addition unit content in the polybutadiene unit in the raw rubber is 4.86%, and the trans-1, 4-addition unit content in the raw rubber is 88.62%; the content of 3, 4-addition units and the content of trans 1, 4-addition units in the polyisoprene units are respectively 4.27 percent and 87.39 percent; the Mooney viscosity ML of the raw rubber is 70.5; tg was-78.6 ℃.
Example 6
The relevant process conditions in example 4 were kept unchanged except that 8L of hexane was added; the mixed monomer used in the first stage consists of 300g of butadiene, 800g of isoprene and 2.3mL of divinylbenzene, the added butyl lithium is 12mL, the continuous feeding time of the mixed monomer and NBL is 80min, the polymerization starting temperature is 80 ℃, the highest polymerization temperature is not higher than 90 ℃, the adding amount of isoprene in the second stage is 250mL, and the active chain lithium end capping uses 12mL of hexane solution of tributyltin chloride.
As a result, the number average molecular weight Mn of the raw rubber was found to be 17.8X 104The molecular weight distribution index D is 1.92; the 1, 2-addition unit content in the polybutadiene unit in the raw rubber was 4.74%, and the trans 1, 4-addition unit content was 87.96%; the content of 3, 4-addition units in the polyisoprene units was 4.94%, and the content of trans 1, 4-addition units was 86.89%; the mooney viscosity ML of the raw rubber was 67.4; tg was-82.7 ℃.
Example 7
The BIR and the Supported-AlR prepared in example 1, which contain both micro-blocks and Long-chain blocks3Three samples of catalytically prepared TBIR with Mooney viscosity of 62 and BR-9000 are respectively mixed with NR, and are subjected to mixing and vulcanization according to the formula and the preparation method of the rubber for the base of the tire, so as to obtain the composite material for the base of the tire, and the physical properties of the composite material are shown in Table 1.
TABLE 1 physical Properties of the composite for tire base
Note: the formula is as follows: the material comprises 30 parts of block BIR, 70 parts of NR, 40 parts of carbon black, 18 parts of filling process oil, 20 parts of white carbon black, 693 parts of silicon, 3.0 parts of zinc oxide, 2.0 parts of stearic acid, 40101.5 parts of anti-aging agent, 1.2 parts of anti-aging agent RD, 1.0 part of accelerator NS, 1.8 parts of accelerator CZ and 3.2 parts of sulfur.
From the data in Table 1, it is found that when BIR containing both micro-blocks and long-chain blocks of the present invention is used in combination with NR, it is possible to obtain a rubber compound for a tire base having high elongation, high hardness, high rebound, low heat generation, and aging resistance in the same ratio, as compared with TBIR and BR-9000, respectively.
Example 8
The BIR and the supported titanium-AlR which are prepared in the example 1 and contain micro-blocks and long-chain blocks simultaneously3Three samples of catalytically prepared TBIR (trans-butadiene rubber) with Mooney viscosity of 62 and BR-9000 are respectively matched with NR, and are subjected to mixing and vulcanization according to the tire rubber side formula and the preparation method of the invention, so that the physical properties of the prepared tire side composite material are shown in Table 1.
TABLE 1 physical Properties of tire side composites
Note:
(1) manufactured by TBIR Hippowa Polymer science and technology.
(2) Examples example 1 sample formulation: NR 60 parts; 40 parts of BIR containing micro blocks and long-chain blocks simultaneously; 60 parts of super wear-resistant carbon black; si-693 parts; 10 parts of environment-friendly rubber oil; ZEOSIL 116520 parts; 3 parts of octyl phenolic tackifying resin; 1.5 parts of an accelerator DM; 1.4 parts of accelerator CZ; 4.0 parts of zinc oxide, 2.5 parts of stearic acid, 40101.5 parts of anti-aging agent, 1.2 parts of anti-aging agent RD, 2.0 parts of protective wax and 1.6 parts of sulfur.
As is clear from the data in Table 1, the use of lithium BIR in the present invention, in comparison with TBIR and BR-9000, respectively, and the use of BIR and TBIR containing both a micro block and a long chain block in combination with NR, respectively, makes it possible to obtain a rubber compound for a tire side portion having both high tensile strength and hardness, high rebound, low heat generation, and excellent aging resistance.
Claims (14)
1. A polybutadiene-isoprene rubber containing both micro-blocks and long-chain blocks, characterized in that: having the following expression:
R—BID—Im—F
wherein,
r is an initiator residue;
BID is a random copolymerization block of butadiene, isoprene and divinylbenzene, the random copolymerization block comprises a butadiene homopolymerization micro-block with the polymerization degree of more than or equal to 1 and an isoprene homopolymerization micro-block with the polymerization degree of more than or equal to 1, and the chain lengths of the butadiene homopolymerization micro-block and the isoprene homopolymerization micro-block are in gradient distribution;
d is a divinylbenzene branching unit, and the average branching degree is 1-2.5;
Imis a long-chain isoprene homopolymer block;
f is a polar end capping group;
the polybutadiene-isoprene rubber containing both the micro block and the long chain block has a number average molecular weight Mn of 12-25 × 104The molecular mass distribution index is 1.75-2.20.
2. A polybutadiene-isoprene rubber containing both micro-blocks and long-chain blocks according to claim 1, characterized in that: the polybutadiene-isoprene rubber containing both the micro block and the long-chain block comprises a polyisoprene block with the number average molecular weight of 4000-20000.
3. A polybutadiene-isoprene rubber containing both micro-blocks and long-chain blocks according to claim 1, characterized in that: in the polybutadiene-isoprene rubber containing both the micro block and the long chain block, the number proportion of 1, 2-addition units of butadiene and 3, 4-addition units of isoprene is less than 10%, and the number proportion of trans-addition units of isoprene units and butadiene units is higher than 80%.
4. A polybutadiene-isoprene rubber containing both micro-blocks and long-chain blocks according to any one of claims 1 to 3, wherein: the raw rubber Mooney viscosity ML of the polybutadiene-isoprene rubber containing both the micro block and the long chain block is 50-70.
5. A preparation method of polybutadiene-isoprene rubber containing both micro-block and long-chain block is characterized in that: continuously and slowly adding a mixed monomer of butadiene, isoprene and divinylbenzene and alkyl lithium into an anionic polymerization solution system preheated to an initiation temperature to perform polymerization reaction; after the mixed monomer and the alkyl lithium are added, adding an isoprene monomer into an anion polymerization solution system for chain extension reaction; and after the chain extension reaction is finished, adding a polar end capping agent into an anionic polymerization solution system to carry out end capping reaction, thus obtaining the modified polyurethane.
6. The method for preparing polybutadiene-isoprene rubber containing both micro-blocks and long-chain blocks according to claim 5, wherein:
the ratio of the mass of the butadiene monomer to the total mass of the isoprene monomer in the polymerization reaction and the chain extension reaction is (20-80): 80-20);
the mass percentage content of the divinylbenzene in the mixed monomer is 0.10-0.2%.
7. The method for preparing polybutadiene-isoprene rubber containing both micro-blocks and long-chain blocks according to claim 5, wherein: the mass ratio of the isoprene monomer in the polymerization reaction to the isoprene monomer in the chain extension reaction is (70-90%): 10-30%.
8. The method for preparing polybutadiene-isoprene rubber containing both micro-blocks and long-chain blocks according to claim 5, wherein: the molecular ratio of the divinyl benzene to the alkyl lithium is (1.0-2.5): 1.
9. The method for preparing polybutadiene-isoprene rubber containing both micro-blocks and long-chain blocks according to claim 5, wherein: the anionic polymerization solution system comprises an anisole activator, and the concentration of the anisole activator in the anionic polymerization solution system is 5-10 mg/kg.
10. The method for preparing polybutadiene-isoprene rubber containing both micro-blocks and long-chain blocks according to claim 5, wherein: the anionic polymerization solution system contains at least one solvent of benzene, toluene, cyclohexane and n-hexane.
11. The method for preparing polybutadiene-isoprene rubber containing both micro-blocks and long-chain blocks according to any one of claims 5 to 10, wherein: and continuously adding the mixed monomer of butadiene, isoprene and divinylbenzene and alkyl lithium into an anionic polymerization solution system preheated to 40-90 ℃ for polymerization reaction, wherein the continuous adding time of the mixed monomer and the alkyl lithium is controlled within the range of 40-120 min.
12. The method for preparing polybutadiene-isoprene rubber containing both micro-blocks and long-chain blocks according to claim 5, wherein: the temperature of the chain extension reaction is 80-90 ℃, and the time is 20-25 min.
13. The method for preparing polybutadiene-isoprene rubber containing both micro-blocks and long-chain blocks according to claim 5, wherein: the polar capping agent comprises at least one element of tin, nitrogen, oxygen and silicon, and at least one functional group of halogen, ketone, acid, amine or ester, which can react with active lithium.
14. The method for preparing polybutadiene-isoprene rubber containing both micro-blocks and long-chain blocks according to claim 5, wherein: the temperature of the end capping reaction is 50-85 ℃, and the time is 15-20 min.
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Cited By (2)
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| CN116285034A (en) * | 2022-12-01 | 2023-06-23 | 中国科学院青岛生物能源与过程研究所 | High-damping vibration attenuation rubber composite material and preparation method and application thereof |
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