CN116813839A - 1,2/3, 4-structured butadiene/isoprene copolymer and preparation method and application thereof - Google Patents
1,2/3, 4-structured butadiene/isoprene copolymer and preparation method and application thereof Download PDFInfo
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- CN116813839A CN116813839A CN202310966603.6A CN202310966603A CN116813839A CN 116813839 A CN116813839 A CN 116813839A CN 202310966603 A CN202310966603 A CN 202310966603A CN 116813839 A CN116813839 A CN 116813839A
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- butadiene
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 171
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229920001577 copolymer Polymers 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 47
- -1 cyano compound Chemical class 0.000 claims abstract description 37
- 229910052742 iron Inorganic materials 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 12
- 150000002506 iron compounds Chemical class 0.000 claims abstract description 11
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 229920001971 elastomer Polymers 0.000 claims abstract description 6
- 239000005060 rubber Substances 0.000 claims abstract description 6
- 229920000028 Gradient copolymer Polymers 0.000 claims abstract description 4
- 229920005604 random copolymer Polymers 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000005062 Polybutadiene Substances 0.000 claims description 22
- 229920002857 polybutadiene Polymers 0.000 claims description 22
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000009826 distribution Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 229920001195 polyisoprene Polymers 0.000 claims description 13
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 claims description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 8
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- WUQVMHPQRIQJMG-UHFFFAOYSA-L iron(2+);6-methylheptanoate Chemical compound [Fe+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O WUQVMHPQRIQJMG-UHFFFAOYSA-L 0.000 claims description 6
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 claims description 5
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 5
- 229960001826 dimethylphthalate Drugs 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- BUJJNPWRTNNUCG-UHFFFAOYSA-L iron(2+);dibenzoate Chemical compound [Fe+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 BUJJNPWRTNNUCG-UHFFFAOYSA-L 0.000 claims description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 5
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 claims description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 4
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 claims description 4
- 150000004678 hydrides Chemical class 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 3
- ZRNHBOAYYNHVOY-UHFFFAOYSA-K 2-hydroxybenzoate;iron(3+) Chemical compound [Fe+3].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O ZRNHBOAYYNHVOY-UHFFFAOYSA-K 0.000 claims description 2
- SLEMZXQMOMKPCD-UHFFFAOYSA-L 7,7-dimethyloctanoate;iron(2+) Chemical compound [Fe+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O SLEMZXQMOMKPCD-UHFFFAOYSA-L 0.000 claims description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrocyanic acid Natural products N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 2
- XWVQUJDBOICHGH-UHFFFAOYSA-N dioctyl nonanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCC(=O)OCCCCCCCC XWVQUJDBOICHGH-UHFFFAOYSA-N 0.000 claims description 2
- GIFIIAHOGINLJV-UHFFFAOYSA-K hexadecanoate;iron(3+) Chemical compound [Fe+3].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GIFIIAHOGINLJV-UHFFFAOYSA-K 0.000 claims description 2
- FRVCGRDGKAINSV-UHFFFAOYSA-L iron(2+);octadecanoate Chemical compound [Fe+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O FRVCGRDGKAINSV-UHFFFAOYSA-L 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 150000002899 organoaluminium compounds Chemical class 0.000 claims description 2
- 150000003021 phthalic acid derivatives Chemical class 0.000 claims description 2
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000005846 sugar alcohols Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 229920001400 block copolymer Polymers 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000914 diffusion-ordered spectroscopy Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction 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
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 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
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of copolymer synthesis, and relates to a 1,2/3, 4-structured butadiene/isoprene copolymer, and a preparation method and application thereof, wherein the preparation method comprises the following steps: under the polymerization conditions of nitrogen atmosphere, certain temperature and pressure, catalyzing butadiene and isoprene by using an iron-based catalyst to carry out copolymerization, and condensing and drying the product to obtain the butadiene/isoprene copolymer. Wherein the iron-based catalyst consists of an organic iron compound, a cyano compound, an ester compound and an organic aluminum compound. The method comprises the steps of catalyzing butadiene and isoprene to carry out copolymerization by utilizing an iron-based catalyst to obtain a copolymer, wherein three modes of simultaneous feeding, sequential feeding and continuous feeding are adopted in the polymerization process to respectively obtain butadiene/isoprene random, block and gradient copolymers; the preparation method is efficient, convenient and fast, has strong practicability, and the prepared butadiene/isoprene copolymer is applied to rubber products and high-performance green tire materials.
Description
Technical Field
The invention belongs to the technical field of copolymer synthesis, and particularly relates to a 1,2/3, 4-structured butadiene/isoprene copolymer, and a preparation method and application thereof.
Background
Compared with polybutadiene and polyisoprene homopolymers, the copolymer of butadiene and isoprene has more advantages in certain properties, for example, the cis-1, 4-structure butadiene/isoprene copolymer shows more excellent low-temperature properties than cis-1, 4-polybutadiene and cis-1, 4-polyisoprene homopolymers, the trans-1, 4-structure butadiene/isoprene copolymer shows more excellent toughness and processability than the homopolymers thereof, and the high ethylene/propylene-based butadiene/isoprene copolymer, namely the 1, 2-butadiene/3, 4-isoprene copolymer, has better wear resistance, low rolling resistance, high wet skid resistance and other properties, thus having wide application prospects in the fields of rubber products, high-performance tires and the like.
There are relatively few reports currently on the synthesis of 1,2/3, 4-structured butadiene/isoprene copolymers. So far, only Giovanni Ricci CrCl 2 ·(dmpe) 2 MAO catalytic system (1,2Syndiotactic polybutadiene of controlled crystallinity by butadiene-isoprene copolymerization with CrCl 2 ·(dmpe) 2 MAO, polym.Bull.,2002,48,25-31), coCl of Takeshi Shiono 2 (Ph 3 P) 2 MAO catalytic system (Copolymerization of 1,3-Butadiene and Isoprene with Cobalt Dichloride/Methylaluminoxane in the Presence ofTriphenylphosphine, J.Polym.Sci.pol.chem.,2002,40,3086-3092), huajing Al (OPhCH) 3 )( i Bu) 2 /MoO 2 Cl 2 TNPP catalytic system (Preparation of Butadiene-Isoprene Copolymer with High Vinyl Contents by Al (OPhCH) 3 )(i-Bu) 2 /MoO 2 Cl 2 TNPP, polymers,2019,11,527) and the like, which realize 1,2/3, 4-selective copolymerization of butadiene and isoprene, but have the defects of low polymerization activity or high cost, and limit the industrial application of the catalyst. Thus, there is a strong need for a composition that has high activityHighly selective catalytic systems are used to prepare 1,2/3, 4-structured butadiene/isoprene copolymers.
The iron element has the advantages of rich sources, environmental friendliness and low cost, and in the previous research, the subject group successfully realizes 1, 2-selectivity of butadiene and 3, 4-selectivity high-activity homopolymerization of isoprene by utilizing iron-based catalytic systems such as iron isooctanoate/phosphorous acid diester/trialkylaluminum and the like. Based on this, the inventor further optimizes and perfects the previous research, and proposes the invention.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a 1,2/3, 4-structured butadiene/isoprene copolymer, a preparation method and application thereof, wherein the copolymer with the structure is obtained by catalyzing butadiene and isoprene to carry out copolymerization by utilizing an iron-based catalyst, and the feeding mode of butadiene and isoprene in the polymerization process adopts three modes of simultaneous feeding, sequential feeding and continuous feeding to respectively obtain butadiene/isoprene random, block and gradient copolymer; the prepared butadiene/isoprene copolymer is applied to rubber products and high-performance green tire materials.
The technical scheme of the invention is as follows:
a method for preparing a 1,2/3, 4-structured butadiene/isoprene copolymer, comprising the following steps:
under the polymerization condition of 20-180 ℃ and 0-3 MPa, catalyzing butadiene and isoprene to carry out copolymerization by utilizing an iron-based catalyst in nitrogen atmosphere, adding an ethanol solution of hydrochloric acid with the mass concentration of 1% to terminate the polymerization reaction after 0.1-10 h of polymerization, and carrying out condensation and drying on the product after the polymerization is finished to obtain a butadiene/isoprene copolymer;
the butadiene and the isoprene added in the polymerization reaction are in the form of a solution, and the organic solvent selected from the butadiene or isoprene solution is a hydrocarbon organic solvent, preferably an aliphatic hydrocarbon organic solvent or an aromatic hydrocarbon organic solvent; the aliphatic hydrocarbon organic solvent is one or more of cyclohexane, n-hexane, pentane, heptane and octane; the aromatic hydrocarbon organic solvent is one or more of benzene, toluene, ethylbenzene and xylene. When the hydrocarbon organic solvent is two or more of the above specific choices, the present invention does not particularly limit the ratio of the above specific substances, and any ratio may be used.
The copolymer is catalyzed and synthesized by adopting an iron-based catalyst; wherein the iron-based catalyst consists of an organic iron compound, a cyano compound, an ester compound and an organic aluminum compound;
in the polymerization process, when the iron-based catalyst is used for catalyzing the copolymerization of butadiene and isoprene, the addition mode of the butadiene, the isoprene and the iron-based catalyst can be any one of the following three modes:
(1) The method of simultaneous feeding is adopted, namely, butadiene and isoprene are simultaneously added into an iron-based catalyst according to a certain molar ratio for polymerization, so as to obtain a butadiene/isoprene random copolymer;
(2) Adopting a sequential feeding method, namely adding any monomer of butadiene and isoprene into an iron-based catalyst for polymerization, and then adding the other monomer for two-stage polymerization to obtain a butadiene/isoprene segmented copolymer;
(3) The continuous feeding method is adopted, namely, any monomer of butadiene and isoprene is firstly added into an iron-based catalyst, and the other monomer is continuously added into a polymerization system at a certain feeding rate during polymerization, so that the butadiene/isoprene gradient copolymer is controlled to be generated.
In the third mode, namely the continuous feeding method, when any monomer is added into the iron-based catalyst for polymerization, the other monomer is continuously added into the polymerization system at a certain feeding rate by a constant flow pump, and at the moment, the certain feeding rate is 0.01-20, preferably 0.1-10, of the first monomer amount per hour.
Further, the molar ratio of butadiene to isoprene is any ratio in the range of 10:90 to 90:10, for example, may be 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20 or 90:10, and may be any ratio in the range;
the molar ratio of the organic iron compound to the two monomers of butadiene and isoprene is 1 (100-100000), namely the amount of the two monomers (butadiene and isoprene) is 100-1 multiplied by 10 compared with the organic iron compound 5 ；
The molar ratio of the organoiron compound to the two monomers (butadiene and isoprene) may be any ratio in the range of 1 (100 to 100000), for example, 1:100, 1:200, 1:500, 1:700, 1:1000, 1:3000, 1:5000, 1:10000, 1:50000, 1:70000, or 1:100000, or any ratio in the range.
Further, in the iron-based catalyst, the molar ratio of the organic iron compound to the cyano compound to the organic aluminum compound is 1 (0.5-20): 0.1-100): 5-100;
preferably, the molar ratio of the organoiron compound to the cyano compound to the ester compound to the organoaluminium compound is 1 (1-5): 1-40): 10-50.
The molar ratio of the organoiron compound, the cyano compound, the ester compound and the organoaluminum compound is 1 (0.5-20): 0.1-100): any ratio in the range of 5-100, for example, may be 1:0.5:0.1:5, 1:20:100:100, 1:10:50:52, 1:1:1:10, 1:5:40:50, 1:3:20:30, and may be 1:2:10:20, 1:2:10:21, 1:3:20:30, 1:3:15:20, 1:4:20:40, or the like.
Further, the temperature is 40-120 ℃, and the polymerization time is 0.5-5 h.
The temperature is any temperature value in the range of 20 to 180 ℃, preferably 40 to 120 ℃, and may be, for example, 20 ℃,30 ℃,40 ℃, 45 ℃,50 ℃, 55 ℃, 60 ℃, 70 ℃,100 ℃,120 ℃, 150 ℃, 160 ℃, 180 ℃, or the like;
the polymerization time is any time in the range of 0.1 to 10 hours, preferably any time in the range of 0.5 to 5 hours, and may be, for example, 0.1 hours, 0.3 hours, 0.5 hours, 0.7 hours, 1.0 hours, 1.5 hours, 2.0 hours, 2.5 hours, 3.0 hours, 5.0 hours, 7.0 hours, 8.5 hours, 10 hours, or the like.
Further, the organic iron compound is organic acid iron containing 1-20 carbon atoms;
preferably, the organic iron compound is any one or more of iron benzoate, iron acetate, iron naphthenate, iron octoate, iron neodecanoate, iron isooctanoate, iron palmitate, iron stearate, iron acetylacetonate and iron salicylate.
Further, the cyano compound is any one or more of azodiisobutyronitrile, azodiisovaleronitrile, azodiisoheptanenitrile and azodicyclohexyl carbonitrile.
Further, the ester compounds comprise aliphatic dibasic acid esters, benzoate esters, phthalic acid esters, benzene polyacid esters, polyol esters, citric acid esters and polyesters;
preferably, the ester compound is any one or more of dioctyl adipate, dioctyl azelate, dioctyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, di-n-octyl phthalate, diisobutyl phthalate and di (2-ethylhexyl) phthalate.
Further, the organic aluminum compound is one or more of trialkylaluminum, dialkylaluminum hydride or methylaluminoxane, and the structural formula of the trialkylaluminum is (R 1 ) 3 Al，R 1 Aliphatic groups represented by carbon atoms 1 to 20; the dialkylaluminum hydride has the structural formula (R) 2 ) 2 AlH，R 2 Aliphatic groups represented by carbon atoms 1 to 20;
preferably, the organic aluminum compound is one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride and methylaluminoxane.
The invention also protects a 1,2/3, 4-structure butadiene/isoprene copolymer, which is prepared by adopting the preparation method;
the butadiene/isoprene copolymer consists of 10-90% of butadiene monomer units and 10-90% of isoprene monomer units in mole fraction, wherein the 1, 2-structure content of the polybutadiene chain segment and the 3, 4-structure content of the polyisoprene chain segment are bothNot less than 50%, the number average molecular weight of the butadiene/isoprene copolymer being 1X 10 3 ～1×10 6 g/mol, molecular weight distribution (M w /M n ) 1.5 to 10.0.
The invention also provides application of the 1,2/3, 4-structured butadiene/isoprene copolymer in rubber products or tires. Namely, the prepared butadiene/isoprene copolymer can be used in the fields of rubber products, high-performance tires and the like.
The invention has the beneficial effects that:
according to the preparation method of the 1,2/3, 4-structure butadiene/isoprene copolymer, an iron-based catalytic system is adopted, iron element is used as active center metal, cyano compounds play a role in coordination with the center metal, organic aluminum compounds play an alkylation role, and ester compounds play a role in the polymer, so that the mobility of a growing molecular chain can be improved, the interaction among the growing molecular chains can be reduced, gel in a product can be prevented, the Mooney viscosity can be reduced, and the later processing performance of the material can be improved.
The iron-based catalyst adopted by the invention has the advantages of high activity and strong selectivity in the aspect of catalyzing butadiene/isoprene copolymerization, ensures the high efficiency and convenience and strong practicability of the preparation method of the butadiene/isoprene copolymer, and is beneficial to realizing large-scale industrial production of the butadiene/isoprene copolymer; the obtained copolymer is a high-performance green tire material with high wet skid resistance, low rolling resistance, high elasticity and high wear resistance.
Drawings
FIG. 1 is a GPC chart of a butadiene/isoprene copolymer prepared in example 1;
FIG. 2 is a DOSY diagram of the butadiene/isoprene copolymer prepared in example 1;
FIG. 3 is a FTIR chart of a butadiene/isoprene copolymer prepared in example 1;
FIG. 4 is a block diagram of a butadiene/isoprene copolymer prepared in example 1 1 HNMR diagram;
FIG. 5 is a GPC chart of the first stage polymer of the block copolymer prepared in example 2 and the diblock copolymer.
Detailed Description
For a further understanding of the present invention, reference will now be made in detail to the present embodiments of the invention, examples of which are illustrated in the accompanying drawings; it will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The following examples, in which no specific conditions are noted, are laboratory routine or routine procedures; unless otherwise indicated, all reagents or apparatus used are conventional products commercially available.
The respective components (organoiron compound, cyano compound, ester compound and organoaluminum compound) of the iron catalyst used in the following examples may be added to the polymerization system in any order, for example, the organoiron compound, cyano compound, ester compound and organoaluminum compound may be added in this order, the organoiron compound, ester compound, cyano compound and organoaluminum compound may be added in this order, or the above-mentioned four components may be mixed and aged before being added to the polymerization system.
Example 1
The embodiment adopts a simultaneous feeding method, and comprises the following specific steps:
to a dry 100mL Schlenk flask, 50mL of a monomer solution of butadiene having a concentration of 0.1g/mL and 50mL of a monomer solution of isoprene having a concentration of 0.126g/mL were added under a nitrogen atmosphere, followed by sequentially adding iron isooctanoate (0.032 mmol), azobisisobutyronitrile (0.064 mmol), dioctyl adipate (0.32 mmol) and triethylaluminum (0.652 mmol), polymerizing in a constant temperature water bath at 50℃for 2 hours, adding an ethanol solution of HCl having a mass concentration of 1% to terminate the polymerization, filtering, and drying the coagulated product to a constant weight under a vacuum atmosphere at 50℃to obtain a butadiene/isoprene copolymer. The polymer yield was 99.0%.
The butadiene/isoprene copolymer produced was characterized. The GPC chart of the copolymer shown in FIG. 1 shows that the copolymer exhibits a unimodal distribution with a number average molecular weight of 24.1X10 -4 A molecular weight distribution of 2.39; the DOSY spectra shown in fig. 2 exhibit a single diffusion coefficient, and the results above all demonstrate that the resulting polymer is a copolymer rather than a blend. The structure of the copolymer is determined to be predominantly 1,2 and 3, 4-structures by the FTIR spectrum shown in fig. 3. By the method shown in FIG. 4 1 The H NMR spectrum can be calculated as follows: the polybutadiene fraction was 50.6%, the 1, 2-structure content in the polybutadiene block was 76.6%, the polyisoprene fraction was 49.4%, and the 3, 4-structure content was 53.4%.
Example 2
This example differs from example 1 in that butadiene, isoprene and iron-based catalyst were added by sequential feeding. The rest steps and parameters are the same as in example 1. The method comprises the following specific steps:
to a dried 100mL Schlenk reaction flask, 50mL of an isoprene monomer solution having a concentration of 0.126g/mL was added under a nitrogen atmosphere, followed by sequentially adding iron isooctanoate (0.032 mmol), azobisisobutyronitrile (0.064 mmol), dioctyl adipate (0.32 mmol) and triethylaluminum (0.652 mmol), polymerizing in a constant temperature water bath at 50℃for 2 hours, adding 50mL of a butadiene monomer solution having a concentration of 0.1g/mL, continuing the polymerization in a constant temperature water bath at 50℃for 2 hours, adding an ethanol solution of HCl having a mass concentration of 1% to terminate the polymerization, filtering, and drying the coagulated product to a constant weight in a vacuum atmosphere at 50℃to obtain a butadiene/isoprene copolymer. The polymer yield was 96.2%.
As can be seen from the GPC curves shown in FIG. 5, the curves of the first stage polymer and the block polymer both show unimodal distribution, and the block polymer curves have a distinct leftwards shift compared with the first stage polymer, demonstrating the increase in molecular weight, and the above solution can prove that a clear block polymer is obtained. The structural parameters of the polymer are as follows:
the polybutadiene fraction was 51.3%, the 1, 2-structure content in the polybutadiene block was 76.2%, and the polyisoprene fraction48.7% by weight, 55.7% by weight of 3, 4-structure, 13.1X10% by weight of the first-stage polyisoprene homopolymer -4 The molecular weight distribution was 2.38, and the number average molecular weight of the block copolymer was 28.6X10 -4 The molecular weight distribution was 2.75.
Example 3
This example differs from example 1 in that a continuous feeding method is employed. The rest steps and parameters are the same as in example 1. The method comprises the following specific steps:
to a dry 100mL Schlenk flask, 50mL of a butadiene monomer solution having a concentration of 0.1g/mL was added under nitrogen atmosphere, followed by sequential addition of iron isooctanoate (0.032 mmol), azobisisobutyronitrile (0.064 mmol), dioctyl adipate (0.32 mmol) and triethylaluminum (0.652 mmol), and polymerization was started in a constant temperature water bath at 50℃while an isoprene solution having a concentration of 0.126g/mL was slowly added to the system by a metering device, the introduction amount was controlled at 50mL for half an hour, and after continuing the polymerization of the system for 2 hours, an ethanol solution of HCl having a mass concentration of 1% was added to terminate the polymerization, filtration was performed, and the coagulated product was dried to constant weight under a vacuum atmosphere at 50℃to obtain a butadiene/isoprene copolymer.
The polymer yield was 94.2%, the polybutadiene fraction was 50.8%, the 1, 2-structure content in the polybutadiene block was 76.9%, the polyisoprene fraction was 49.2%, the 3, 4-structure content was 52.4%, and the number average molecular weight was 22.5X10 -4 The molecular weight distribution was 2.43.
Example 4
The method adopts a simultaneous feeding method, and comprises the following specific steps:
to a dry 100mL Schlenk flask, 80mL of a monomer solution of butadiene having a concentration of 0.1g/mL and 20mL of a monomer solution of isoprene having a concentration of 0.126g/mL were added under a nitrogen atmosphere, followed by successively adding iron acetylacetonate (0.033 mmol), azobisisobutyronitrile (0.066 mmol), dioctyl adipate (0.33 mmol) and triethylaluminum (1.650 mmol), polymerizing in a constant temperature water bath at 50℃for 2 hours, adding an ethanol solution of HCl having a mass concentration of 1% to terminate the polymerization, filtering, and drying the coagulated product to a constant weight under a vacuum atmosphere at 50℃to obtain a butadiene/isoprene copolymer.
The polymer yield was 94.1%, the polybutadiene fraction was 80.5%, the 1, 2-structure content in the polybutadiene block was 78.6%, the polyisoprene fraction was 19.5%, the 3, 4-structure content therein was 57.2%, and the number average molecular weight was 26.3X10 -4 The molecular weight distribution was 2.47.
Example 5
The material feeding method comprises the following specific steps:
to a dried 100mL Schlenk reaction flask, 20mL of an isoprene monomer solution having a concentration of 0.126g/mL was added under a nitrogen atmosphere, followed by successively adding ferric acetylacetonate (0.033 mmol), azobisisobutyronitrile (0.066 mmol), dioctyl adipate (0.33 mmol) and triethylaluminum (1.650 mmol), polymerizing in a constant temperature water bath at 50℃for 2 hours, adding 80mL of a butadiene monomer solution having a concentration of 0.1g/mL, continuing the polymerization in a constant temperature water bath at 50℃for 2 hours, adding an ethanol solution of HCl having a mass concentration of 1% to terminate the polymerization, filtering, and drying the coagulated product to a constant weight in a vacuum atmosphere at 50℃to obtain a butadiene/isoprene copolymer.
The polymer yield was 94.1%, the polybutadiene fraction was 81.1%, the 1, 2-structure content in the polybutadiene block was 78.8%, the polyisoprene fraction was 18.9%, the 3, 4-structure content was 54.7%, and the number average molecular weight was 25.6X10 -4 The molecular weight distribution was 2.58.
Example 6
The continuous feeding method comprises the following specific steps:
to a dry 100mL Schlenk flask, 80mL of a butadiene monomer solution having a concentration of 0.1g/mL was added under nitrogen atmosphere, followed by sequentially adding ferric acetylacetonate (0.033 mmol), azobisisobutyronitrile (0.066 mmol), dioctyl adipate (0.33 mmol) and triethylaluminum (1.650 mmol), and the mixture was placed in a constant temperature water bath at 50℃to initiate polymerization, while an isoprene solution having a concentration of 0.126g/mL was slowly added to the system by a metering device, the introduction amount was controlled at 20mL for half an hour, and after continuing the polymerization of the system for 2 hours, an ethanol solution of HCl having a mass concentration of 1% was added to terminate the polymerization, filtration was carried out, and the coagulated product was dried to constant weight under a vacuum atmosphere at 50℃to obtain a butadiene/isoprene copolymer.
95.1% of the polymer, 80.7% of the polybutadiene fraction, 77.9% of the 1, 2-structure content of the polybutadiene block, 19.3% of the polyisoprene fraction, 54.6% of the 3, 4-structure content, and a number average molecular weight of 28.1X10 -4 The molecular weight distribution was 2.39.
Example 7
The embodiment adopts a simultaneous feeding method, and comprises the following specific steps:
to a dry 100mL Schlenk flask, 90mL of a butadiene monomer solution having a concentration of 0.10g/mL and 10mL of an isoprene monomer solution having a concentration of 0.126g/mL were added under a nitrogen atmosphere, followed by successively adding iron benzoate (0.032 mmol), azobisisovaleronitrile (0.096 mmol), dimethyl phthalate (0.64 mmol) and diethylaluminum hydride (0.96 mmol), polymerizing in a water bath at a constant temperature of 100℃for 4 hours, adding an ethanol solution of HCl having a mass concentration of 1% to terminate the polymerization, filtering, and drying the coagulated product to a constant weight under a vacuum atmosphere at 50℃to obtain a butadiene/isoprene copolymer.
92.1% of the polymer, 91.2% of the polybutadiene fraction, 78.9% of the 1, 2-structure content in the polybutadiene block, 8.8% of the polyisoprene fraction, 55.6% of the 3, 4-structure content, and a number average molecular weight of 26.1X10 -4 The molecular weight distribution was 2.39.
Example 8
The embodiment adopts a simultaneous feeding method, and comprises the following specific steps:
to a dry 100mL Schlenk flask, 70mL of a butadiene monomer solution having a concentration of 0.10g/mL and 30mL of an isoprene monomer solution having a concentration of 0.126g/mL were added under a nitrogen atmosphere, followed by successively adding iron benzoate (0.032 mmol), azobisisovaleronitrile (0.32 mmol), dimethyl phthalate (1.6 mmol) and diethylaluminum hydride (1.76 mmol), and after polymerization in a water bath at a constant temperature of 120℃for 1 hour, an ethanol solution of HCl having a mass concentration of 1% was added to terminate the polymerization, filtration was carried out, and the coagulated product was dried under a vacuum atmosphere at 50℃until a constant weight was obtained.
91.5% of the polymer, 70.5% of the polybutadiene fraction, 76.9% of the 1, 2-structure content of the polybutadiene block, 29.5% of the polyisoprene fraction, 54.5% of the 3, 4-structure content, and 23.1X10% of the number average molecular weight -4 The molecular weight distribution was 2.54.
Example 9
The embodiment adopts a simultaneous feeding method, and comprises the following specific steps:
to a dry 100mL Schlenk flask, 10mL of a butadiene monomer solution having a concentration of 0.10g/mL and 90mL of an isoprene monomer solution having a concentration of 0.126g/mL were added under a nitrogen atmosphere, followed by successively adding iron benzoate (0.032 mmol), azobisisovaleronitrile (0.032 mmol), dimethyl phthalate (0.032 mmol) and diethylaluminum hydride (0.32 mmol), and after polymerization in a 40℃constant temperature water bath for 10 hours, an ethanol solution of HCl having a mass concentration of 1% was added to terminate the polymerization, filtration was carried out, and the coagulated product was dried to a constant weight under a vacuum atmosphere at 50℃to obtain a butadiene/isoprene copolymer.
92.3% of the polymer, 11.1% of the polybutadiene fraction, 74.1% of the 1, 2-structure content in the polybutadiene block, 88.9% of the polyisoprene fraction, 53.1% of the 3, 4-structure content, and 23.5X10 number average molecular weight -4 The molecular weight distribution was 2.37.
The foregoing description is only a preferred embodiment of the present invention and is not intended to limit the present invention, but although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or that equivalents may be substituted for part of the technical features thereof. Any modification, equivalent replacement, variation, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing a 1,2/3, 4-structured butadiene/isoprene copolymer, comprising the steps of:
under the polymerization condition of 20-180 ℃ and 0-3 MPa, catalyzing butadiene and isoprene to carry out copolymerization by utilizing an iron-based catalyst in nitrogen atmosphere, adding an ethanol solution of hydrochloric acid with the mass concentration of 1% to terminate the polymerization reaction after 0.1-10 h of polymerization, and carrying out condensation and drying on the product after the polymerization is finished to obtain a butadiene/isoprene copolymer;
wherein the iron-based catalyst consists of an organic iron compound, a cyano compound, an ester compound and an organic aluminum compound;
the adding modes of the butadiene, isoprene and iron-based catalyst comprise the following three modes:
(1) Simultaneously feeding; adding butadiene and isoprene into an iron-based catalyst simultaneously for polymerization to obtain a butadiene/isoprene random copolymer;
(2) A feeding method is carried out sequentially; adding any monomer of butadiene and isoprene into an iron-based catalyst for polymerization, and then adding the other monomer for two-stage polymerization to obtain a butadiene/isoprene segmented copolymer;
(3) A continuous feeding method; adding any monomer of butadiene and isoprene into an iron-based catalyst, and continuously adding the other monomer into a polymerization system at a certain feeding rate during polymerization to obtain the butadiene/isoprene gradient copolymer.
2. The method according to claim 1, wherein the molar ratio of butadiene to isoprene is 10:90 to 90:10; the molar ratio of the organic iron compound to the two monomers of butadiene and isoprene is 1 (100-100000).
3. The preparation method according to claim 1, wherein the molar ratio of the organoiron compound, the cyano compound, the ester compound and the organoaluminum compound in the iron-based catalyst is 1 (0.5-20): 0.1-100): 5-100;
preferably, the molar ratio of the organoiron compound to the cyano compound to the ester compound to the organoaluminium compound is 1 (1-5): 1-40): 10-50.
4. The preparation method according to claim 1, wherein the temperature is 40 to 120 ℃ and the polymerization time is 0.5 to 5 hours.
5. The production method according to claim 1, wherein the organic iron compound is an organic acid iron having 1 to 20 carbon atoms;
preferably, the organic iron compound is any one or more of iron benzoate, iron acetate, iron naphthenate, iron octoate, iron neodecanoate, iron isooctanoate, iron palmitate, iron stearate, iron acetylacetonate and iron salicylate.
6. The method according to claim 1, wherein the cyano compound is any one or more of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile and azodicyclohexyl carbonitrile.
7. The method according to claim 1, wherein the ester compound comprises aliphatic dibasic acid esters, benzoic acid esters, phthalic acid esters, benzene polyacid esters, polyhydric alcohol esters, citric acid esters, polyesters;
preferably, the ester compound is any one or more of dioctyl adipate, dioctyl azelate, dioctyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, di-n-octyl phthalate, diisobutyl phthalate and di (2-ethylhexyl) phthalate.
8. The preparation method according to claim 1, wherein the organoaluminum compound is one or more of trialkylaluminum, dialkylaluminum hydride or methylaluminoxane, and the trialkylaluminum has a structural formula (R 1 ) 3 Al，R 1 Aliphatic groups represented by carbon atoms 1 to 20; the dialkylaluminum hydride has the structural formula (R) 2 ) 2 AlH，R 2 Aliphatic groups represented by carbon atoms 1 to 20;
preferably, the organic aluminum compound is one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride and methylaluminoxane.
9. A 1,2/3, 4-structured butadiene/isoprene copolymer, characterized in that it is prepared by the preparation method according to any one of claims 1 to 8;
the butadiene/isoprene copolymer consists of 10-90% of butadiene monomer units and 10-90% of isoprene monomer units in mole fraction, wherein the 1, 2-structure content of the polybutadiene chain segment and the 3, 4-structure content of the polyisoprene chain segment are both more than or equal to 50%, and the number average molecular weight of the butadiene/isoprene copolymer is 1 multiplied by 10 3 ～1×10 6 g/mol, molecular weight distribution (M w /M n ) 1.5 to 10.0.
10. Use of a 1,2/3, 4-structured butadiene/isoprene copolymer according to claim 9 in rubber articles or tires.
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