CN106632764A - Iron-based catalyst, preparation method of iron-based catalyst, and application of iron-based catalyst in isoprene polymerization - Google Patents
Iron-based catalyst, preparation method of iron-based catalyst, and application of iron-based catalyst in isoprene polymerization Download PDFInfo
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Abstract
The invention relates to the technical field of conjugated diene catalytic polymerization, in particular to an iron-based catalyst; the iron-based catalyst comprises a main catalyst and an auxiliary catalyst; the main catalyst is pyridylimine iron complex, the auxiliary catalyst is methylaluminoxane, and a molar ratio of aluminum in the auxiliary catalyst to iron in the main catalyst is 500:1. Application of the iron-based catalyst in isoprene polymerization is also disclosed. The iron-based catalyst of the application has high activity in catalyzing isoprene, the obtained polymer has high molecular weight and narrow molecular weight distribution, the microscopic structure of the polymer may be controlled through cutting the main catalyst structure, the proportion of cis-1,4 structure in isoprene is adjustably in the range of 62.7% to 86.7%, the proportion of trans-1,4 structure is adjustably in the range of 2.8% to 8.2%, and the proportion of 3,4 structure is adjustably in the range of 6.7% to 34.5%. The iron-based catalyst is insensitive to reaction temperature.
Description
Technical field
The present invention relates to conjugated diene catalysis polymerization technology field, and in particular to a kind of Fe-series catalyst, institute is further related to
The preparation method of Fe-series catalyst is stated, Fe-series catalyst is further related to and is prepared HMW and microcosmic knot in catalysis isoprene polymerization
Application in the controllable polyisoprene of structure.
Background technology
Isoprene by Isosorbide-5-Nitrae addition, 1,2 additions and 3,4 additions can synthesizing cis-Isosorbide-5-Nitrae structure, anti-form-1,4 structures,
The polymer of 1,2 structures and 3,4 structures.Microstructural differences determine that polyisoprene has different performances.Such as cis-
The performance of Isosorbide-5-Nitrae structure polyisoprene can be widely used in numerous rubber such as tire, adhesive tape, sebific duct, rubber overshoes similar to natural rubber
Manufacture field, is best one glue kind of combination property in synthetic rubber.Anti-form-1, the performance of 4 structure polyisoprene then class
Gutta-percha is similar to, such rubber has excellent dynamic mechanical, and good dynamic fatigue property and anti-wear performance,
Rolling resistance is minimum in all tire rubber.3,4 polyisoprene are then a kind of high wet-sliding resistants, the synthetic rubber material of low-heat-generation
Material, can be used in tire tread glue to improve security performance.
Catalyst plays key effect in polyisoprene structure and Properties Control, is polyisoprene compound probability
Core content.It is at present industrial it is main using titanium system, lithium system and rare earth series catalysts come synthetic polyisoprenes rubber, it is cis-
1,4 structures are general up to 98%.Additionally, late transition metal catalyst possesses weaker oxytropism due to its metal center, while
Its catalysis obtains polymer architecture and diversity is presented and receives much concern.Wherein Fe-series catalyst is again because of its low price, synthesis letter
It is single, the easy cutting of structure and become important research object.
Hiromichi utilizes earliest Fe-series catalyst Fe (dmg)2/AlEt3Catalysis isoprene polymerization obtains 3,4 structures and is
Main polymer, but yield relatively low (23.2%)【J.Polym.Sci.Polym.Let.,1964,2,593-596】.Ricci is reported
Although the iron catalyst yield in road may be up to 100%, the selectivity of polymer architecture is not high【J.Mol.Catal.A:
Chem.2003,204-205,287-293】.Additionally, Fe-series catalyst catalysis isoprene polymerization, its polymer molecular weight distribution
General wider and microstructure causes the poor controllability for synthesizing to very temperature sensitive, and the polymer architecture for obtaining and performance are not
It is stable, there is industrialization difficulty【Shandong chemical industry 2013,42,65-66】.Therefore, seek high activity and obtain HMW and micro-
Seeing the Novel iron catalyst system and catalyzing of structure adjustable polymer becomes a challenge of academia.
Changchun applied chemistry study Zhang Xuequan be prepared for fragrant cyclosubstituted pyridine imine cobalt complex in AlEtCl2It is living
Change the lower Isosorbide-5-Nitrae structure polybutadiene for being used for 1,3 polymerizing butadienes, obtaining higher yield and high-load【Polyemrs
2016,8,12】.But the iron catalyst of correlation synthesizes and is not directed to for isoprene polymerization.It is sub- that Ritter reports pyridine
Amine iron complex is in alkyl aluminum and alkylation removal reagent [Ph3C]+[B(C6F5)4]-The lower catalysis isoprene high selectivity of activation is gathered
Close【Angew.Chem.Int.Ed.2012,51,11805-11808.】.Substituent obtains major part with anti-form-1 when being octyl group, and 4
The polymer that structure is present, and when triphenylbenzene of the substituent for aromatic ring, the polymer for obtaining is mainly with cis-Isosorbide-5-Nitrae structure
Exist.It is probably what is caused by electronic effect that this phenomenon is mentioned in document.Due to only having investigated two catalyst to polymerization
The impact of structure, it is difficult to determine Molecular level, also cannot carry out regulation and control in larger scope to catalyst microstructure
So that polymer performance is presented diversity, while alkylation removal reagent [Ph3C]+[B(C6F5)4]-Use substantially increase catalysis
Agent cost.
The content of the invention
The polymer point of the synthesis that the catalyst in order to solve above prior art used in isoprene polymerization is present
Son amount is distributed width, high cost, regulation and control in larger scope cannot be carried out to catalyst microstructure so that polymer performance is presented
Multifarious problem, this application provides a kind of new Fe-series catalyst, pyridine imine iron complex is used as major catalyst,
Under industrialized co-catalyst MAO (MAO) activation of Jing, isoprene polymerization is catalyzed, shows higher catalysis and live
Property, and HMW and the adjustable polymer of microstructure have been obtained, the microstructure of polymer can be tied by major catalyst
The cutting of structure is regulated and controled, and insensitive to reaction temperature.
Present invention also offers the preparation method of the Fe-series catalyst.
Present invention also offers the application in the Fe-series catalyst isoprene polymerization.
What the present invention was obtained through the following steps：
A kind of Fe-series catalyst, is made up of major catalyst and co-catalyst,
Major catalyst is pyridine imine iron complex, and its general structure is as follows：
In formula, X is halogen (Cl or Br)；R1ForR2For hydrogen (- H), methyl
(-CH3), ethyl (- CH2CH3) or phenyl (- Ph)；R3For hydrogen (- H), alkyl (methyl etc.), aryl (phenyl, naphthyl etc.) or halogen
Plain (Br, Cl etc.)；The complex passes through adjusted and controlled, especially the electronic effect of the substituent of nitrogen connection and steric hindrance effect on imines
Should, the catalysis activity of catalyst can be increased, while the molecular weight of polymer can be effectively improved and micmstructure of polymer is realized
Regulation and control；
Co-catalyst is MAO, and general structure isWherein n is the natural number of 4-40；
The mol ratio of the ferro element in aluminium element and major catalyst in co-catalyst is 500:1.
Described Fe-series catalyst, X is Br or Cl, R in preferred pyridine imine iron complex2For-H；R3For-H.
Described Fe-series catalyst, X is Cl in preferred pyridine imine iron complex structural formula；R1For adamantyl, triphen
Methyl or 2,6- bis- (benzhydryl) -4- aminomethyl phenyls；R2For hydrogen (- H)；R3For hydrogen (- H)；Structural formula is
The preparation method of major catalyst pyridine imine iron complex in described Fe-series catalyst, at room temperature, by pyridine
Imine ligand is reacted with the halide of iron in dichloromethane solvent with equimolar ratio, through post processing, is obtained final product.Post-processing operation
To be filtrated to get product and being washed with n-hexane three times, it is dried to constant weight.
Application of the described Fe-series catalyst in isoprene polymerization.
Described application, preferably by co-catalyst, after toluene and isoprene are separately added into, adds the two of major catalyst
Chloromethanes solution carries out polymerisation so as to obtain polyisoprene.
Described application, preferred monomers isoprene is with the mol ratio of ferro element in major catalyst in Fe-series catalyst
2500：1.
Described application, the temperature of preferred polymeric reaction is -25～25 DEG C, and polymerization time is 2 hours.
Described application, the polyisoprene number-average molecular weight for obtaining is high, is 6.1 × 104-28.2×104, molecular weight point
Cloth is narrow, is 1.61-2.08.
Described application, according to adding major catalyst species different, its microstructure is adjustable and to temperature-insensitive, obtains
Polyisoprene in cis-Isosorbide-5-Nitrae structure proportion adjustable extent be 62.7%～86.7%, anti-form-1,4 structure institute accountings
Example adjustable extent is 2.8%～8.2%, and 3,4 structure proportion adjustable extents are 6.7%～34.5%.
Beneficial effects of the present invention：
1) the major catalyst preparation method in the Fe-series catalyst of the application is simple, with low cost；Co-catalyst is methyl
Aikyiaiurnirsoxan beta (MAO), relative to alkylation removal reagent (Ph used in background technology3C+B(C6F5)4 -), it is more cheap and easy to get；
2) the Fe-series catalyst catalysis isoprene of the application shows as higher activity, the polymer molecular weight for obtaining
Height, 6.1 × 104-28.2×104, narrow molecular weight distribution, 1.61-2.08, while the microstructure of polymer can pass through main catalytic
The cutting of agent structure is regulated and controled, and cis in isoprene-Isosorbide-5-Nitrae structure proportion adjustable extent is 62.7%～86.7%,
Anti-form-1,4 structure proportion adjustable extents be 2.8%～8.2%, 3,4 structure proportion adjustable extents be 6.7%～
34.5%.
3) Fe-series catalyst of the application is insensitive to reaction temperature, change temperature on micmstructure of polymer affect compared with
It is little, therefore with good industrial value.
Description of the drawings
Fig. 1 is the complex mass spectrogram that embodiment 1 is obtained,
Fig. 2 is the complex mass spectrogram that embodiment 2 is obtained,
Fig. 3 is the complex mass spectrogram that embodiment 3 is obtained.
Specific embodiment
The present invention is further described with reference to specific embodiment：
First, major catalyst pyridine imine iron complex is prepared
Embodiment 1
The present embodiment prepares pyridine imine iron complex shown in formula (I)：
Under nitrogen atmosphere, the pyrrole for adding the adamantyl of equimolar ratio to replace in dry Xi Laike (Schlenk) pipe
Pyridine imine ligand and anhydrous FeCl2, add 10mlCH2Cl2 and stir 24 hours under room temperature (about 20 DEG C, as follows), product
Filter and washed with 10ml n-hexanes, wash three times, be dried under vacuum to constant weight, obtain orange solids 0.35g, i.e. the present embodiment
Target product, yield 95%.
Mass spectral analysis：Theoretical value：C16H20ClFeN2:331.0664, measured value:330.9991 [M-Cl]+(Fig. 1).
Elementary analysis result：Theoretical value：C16H20Cl2FeN2:C, 52.35%；H, 5.49%；N, 7.63%；Measured value:
C, 52.58%；H, 5.34%；N, 7.38%.
Infrared analysis：IR(KBr)/cm-1:1588, ν (C=N).
Embodiment 2
Pyridine imine iron complex shown in formula (II) prepared by the present embodiment, wherein R1 '=H, R2 '=H, preparation process
It is specific as follows：Under nitrogen atmosphere, the pyrrole for adding the trityl of equimolar ratio to replace in dry Xi Laike (Schlenk) pipe
Pyridine imine ligand and anhydrous FeCl2, add 10mlCH2Cl2 and are stirred at room temperature 24 hours, product filter and with 10ml just oneself
Alkane is washed, and is washed three times, is dried under vacuum to constant weight, obtains the target product of light pink solid 0.46g, i.e. the present embodiment, yield
96%.Mass spectral analysis：Theoretical value：C25H20ClFeN2:439.0664, measured value:439.0714 [M-Cl]+(Fig. 2).
Elementary analysis result：Theoretical value：C25H20Cl2FeN2:C, 63.19%；H, 4.24%；N, 5.90%；Measured value:
C, 62.92%；H, 4.19%；N, 5.72%.
Infrared analysis：IR(KBr)/cm-1:1587, ν (C=N).
Embodiment 3
Pyridine imine iron complex shown in formula (III) prepared by the present embodiment, wherein R1 "=H, R2 "=H, R3 "=
CH3, preparation process is specific as follows：
Under nitrogen atmosphere, in dry Xi Laike (Schlenk) pipe add equimolar ratio 2,6- bis- (benzhydryl)-
Pyridine imine ligand and anhydrous FeCl2 that 4- aminomethyl phenyls replace, add 10mlCH2Cl2 and are stirred at room temperature 24 hours, produce
Thing is filtered and washed with 10ml n-hexanes, is washed three times, is dried under vacuum to constant weight, obtains claret solid 0.61g, i.e. this enforcement
The target product of example, yield 93%.
Mass spectral analysis：Theoretical value：C39H32ClFeN2:619.1603, measured value:619.0020 [M-Cl]+(Fig. 3).
Elementary analysis result：Theoretical value：C39H32Cl2FeN2:C, 71.47%；H, 4.92%；N, 4.27%；Measured value:
C, 71.98%；
H, 4.88%；N, 4.18%.
Infrared analysis：IR(KBr)/cm-1:1593, ν (C=N).
2nd, isoprene polymerization reaction
Embodiment 4
Under nitrogen atmosphere, in uncommon Rec (Schlenk) pipes of 50ml, triisobutyl aluminium (TIBA) 4mmol is added, it is anhydrous
Toluene 7ml, isoprene 2ml (20.0mmol), use 1ml CH2Cl2The catalyst 2.9mg (8 that the embodiment 1 of dissolving is prepared
μm ol), be polymerized 2h at 25 DEG C, the reaction ethanol watery hydrochloric acid (50 of 20ml:1) solution terminates, and does not obtain polymer.Using
Without polymerization activity in the case of co-catalyst triisobutyl aluminium.
Embodiment 5
Under nitrogen atmosphere, in uncommon Rec (Schlenk) pipes of 50ml, diethylaluminum chloride (AlEt is added2Cl)
4mmol, dry toluene 7ml, isoprene 2ml (20.0mmol), use 1ml CH2Cl2What the embodiment 1 of dissolving was prepared urges
Agent 2.9mg (8 μm of ol), be polymerized 2h at 25 DEG C, the reaction ethanol watery hydrochloric acid (50 of 20ml:1) solution terminates, and is gathered
Compound.Without polymerization activity in the case of using co-catalyst diethylaluminum chloride.
Embodiment 6
Under nitrogen atmosphere, in uncommon Rec (Schlenk) pipes of 50ml, ethylaluminium dichloride (AlEtCl is added2)
4mmol, dry toluene 7ml, isoprene 2ml (20.0mmol), use 1ml CH2Cl2What the embodiment 1 of dissolving was prepared urges
Agent 2.9mg (8 μm of ol), be polymerized 2h at 25 DEG C, the reaction ethanol watery hydrochloric acid (50 of 20ml:1) solution terminates, and filters, and uses
Ethanol is washed and constant weight, yield is dried under vacuum under three times, room temperature：53.4%, number-average molecular weight：1800, polydispersity coefficient：4.70.
Resulting polymers molecular weight is 1800 in the case of using co-catalyst ethylaluminium dichloride, far below using methyl in embodiment 9
The molecular weight (7.0 × 10 of resulting polymers when alumina is turned into co-catalyst4)。
Embodiment 7 (embodiment 7-9 is the ratio for screening major catalyst and co-catalyst, respectively 200:1；800:1；
500:1)
Under nitrogen atmosphere, in uncommon Rec (Schlenk) pipes of 50ml, 0.09g (1.6mmol) MAO is added
(MAO), dry toluene 7ml, isoprene 2ml (20.0mmol), use 1ml CH2Cl2What the embodiment 1 of dissolving was prepared urges
Agent 2.9mg (8 μm of ol), be polymerized 2h at 25 DEG C, the reaction ethanol watery hydrochloric acid (50 of 20ml:1) solution terminates, and filters, and uses
Ethanol is washed and constant weight, yield is dried under vacuum under three times, room temperature：12.1%, number-average molecular weight：3.1×104, polydispersity coefficient ()：
2.63.Yield it is relatively low not as preferred pair as.
Embodiment 8
Under nitrogen atmosphere, in uncommon Rec (Schlenk) pipes of 50ml, 0.36g (6.4mmol) MAO is added
(MAO), dry toluene 7ml, isoprene 2ml (20.0mmol), use 1ml CH2Cl2What the embodiment 1 of dissolving was prepared urges
Agent 2.9mg (8 μm of ol), be polymerized 2h at 25 DEG C, the reaction ethanol watery hydrochloric acid (50 of 20ml:1) solution terminates, and filters, and uses
Ethanol is washed and constant weight, yield is dried under vacuum under three times, room temperature：40.1%, number-average molecular weight：1.3×104, polydispersity coefficient：
2.07.Yield is not also high, not as preferred pair as.
Embodiment 9
Under nitrogen atmosphere, in uncommon Rec (Schlenk) pipes of 50ml, 0.23g (4mmol) MAO is added
(MAO), dry toluene 7ml, isoprene 2ml (20.0mmol), use 1ml CH2Cl2What the embodiment 1 of dissolving was prepared urges
Agent 2.9mg (8 μm of ol), be polymerized 2h at 25 DEG C, the reaction ethanol watery hydrochloric acid (50 of 20ml:1) solution terminates, and filters, and uses
Ethanol is washed and constant weight, yield is dried under vacuum under three times, room temperature：58.2%, number-average molecular weight：7.0×104, polydispersity coefficient：
1.82.Different structure proportion：Cis-Isosorbide-5-Nitrae structure accounts for 76.8%, anti-form-1,4 structures account for 8.2% (cis-Isosorbide-5-Nitrae structure with
Anti-form-1, the ratio of 4 structures is 90：10), 3,4 structures account for 15.0%.
Embodiment 10
The catalyst 2.9mg (8 μm of ol) that embodiment 1 used by polymerisation is prepared, other are with embodiment 9, reaction temperature
Spend for -25 DEG C, yield：46.2%, number-average molecular weight：11.2×104, polydispersity coefficient：1.78.Different structure proportion：
Cis-Isosorbide-5-Nitrae structure accounts for 83.4%, anti-form-1, and 4 structures account for 6.2%, and (cis-Isosorbide-5-Nitrae structure and anti-form-1, the ratio of 4 structures is 91：
9), 3,4 structures account for 10.4%.
Embodiment 11
The catalyst 2.9mg (8 μm of ol) that embodiment 1 used by polymerisation is prepared, other are with embodiment 9, reaction temperature
Spend for 0 DEG C, yield：51.2%, number-average molecular weight：8.9×104, polydispersity coefficient：1.81.Different structure proportion：It is suitable
Formula-Isosorbide-5-Nitrae structure accounts for 78.4%, anti-form-1, and 4 structures account for 7.3%, and (cis-Isosorbide-5-Nitrae structure and anti-form-1, the ratio of 4 structures is 91：8),
3,4 structures account for 14.3%.
Can find that impact of the temperature to micmstructure of polymer is less according to embodiment 9-11, at -25-25 DEG C, cis -
The change of Isosorbide-5-Nitrae structure proportion is little, is 76.8～83.4%.
Embodiment 12
The catalyst 3.8mg (8 μm of ol) that embodiment 2 used by polymerisation is prepared, other are with embodiment 9, reaction temperature
Spend for -25 DEG C, yield：50.1%, number-average molecular weight：12.3×104, polydispersity coefficient：2.03.Different structure proportion：
Cis-Isosorbide-5-Nitrae structure accounts for 86.7%, anti-form-1, and 4 structures account for 6.6%, and (cis-Isosorbide-5-Nitrae structure and anti-form-1, the ratio of 4 structures is 91：
9), 3,4 structures account for 6.7%.
Embodiment 13
The catalyst 3.8mg (8 μm of ol) that embodiment 2 used by polymerisation is prepared, other are with embodiment 9, reaction temperature
Spend for 0 DEG C, yield：53.6%, number-average molecular weight：9.6×104, polydispersity coefficient：2.07.Different structure proportion：It is suitable
Formula-Isosorbide-5-Nitrae structure accounts for 83.2%, anti-form-1, and 4 structures account for 7.0%, and (cis-Isosorbide-5-Nitrae structure and anti-form-1, the ratio of 4 structures is 91：
10), 3,4 structures account for 9.8%.
Embodiment 14
The catalyst 3.8mg (8 μm of ol) that embodiment 2 used by polymerisation is prepared, other are with embodiment 9, reaction temperature
Spend for 25 DEG C, yield：61.3%, number-average molecular weight：6.1×104, polydispersity coefficient：2.08.Different structure proportion：It is suitable
Formula-Isosorbide-5-Nitrae structure accounts for 78.2%, anti-form-1, and 4 structures account for 7.6%, and (cis-Isosorbide-5-Nitrae structure and anti-form-1, the ratio of 4 structures is 91：9),
3,4 structures account for 14.2%.
Embodiment 15
The catalyst 5.2mg (8 μm of ol) that embodiment 3 used by polymerisation is prepared, other are with embodiment 9, reaction temperature
Spend for -25 DEG C, yield：73.2%, number-average molecular weight：28.2×104, polydispersity coefficient：1.70.Different structure proportion：
Cis-Isosorbide-5-Nitrae structure accounts for 69.9%, anti-form-1, and 4 structures account for 4.5%, and (cis-Isosorbide-5-Nitrae structure and anti-form-1, the ratio of 4 structures is 94：
6), 3,4 structures account for 25.6%.
Embodiment 16
The catalyst 5.2mg (8 μm of ol) that embodiment 3 used by polymerisation is prepared, other are with embodiment 9, reaction temperature
Spend for 0 DEG C, yield：79.7%, number-average molecular weight：21.6×104, polydispersity coefficient：1.63.Different structure proportion：It is suitable
Formula-Isosorbide-5-Nitrae accounts for 63.9%, anti-form-1, and 4 structures account for 3.0%, and (cis-Isosorbide-5-Nitrae structure and anti-form-1, the ratio of 4 structures is 96：4), 3,4
Structure accounts for 33.1%.
Embodiment 17
The catalyst 5.2mg (8 μm of ol) that embodiment 3 used by polymerisation is prepared, other are with embodiment 9, reaction temperature
Spend for 25 DEG C, yield：85.7%, number-average molecular weight：18.2×104, polydispersity coefficient：1.61.Different structure proportion：It is suitable
Formula-Isosorbide-5-Nitrae structure accounts for 62.7%, anti-form-1, and 4 structures account for 2.8%, and (cis-Isosorbide-5-Nitrae structure and anti-form-1, the ratio of 4 structures is 96：4),
3,4 structures account for 34.5%.
The data of each embodiment arrange such as following table.
Understood by embodiment 9,14,17, regulate and control R1Substituent can cause the structure proportion of polymer Cis formulas -1,4 from 62.7%
Increase to 78.2%, 3,4 structure proportions are reduced to 8.2% from 34.5.
The major catalyst of the present invention can be seen that with the substituent of nitrogen connection on its imines by above-mentioned comparative example
Electronic effect and steric effect difference, the molecular weight and microstructure of controllable resulting polymers, electron-withdrawing substituent and big position
Resistance substituent is conducive to the raising of molecular weight and the increase of 3,4 structures.Additionally, change temperature on micmstructure of polymer affect compared with
It is little.
Above-described embodiment is not limited for the present invention preferably embodiment, but embodiments of the present invention by embodiment
System, other any Spirit Essences and the changes, modification made under principle without departing from the present invention, combines, substitutes, simplifying and should be
Equivalence replacement mode, is included within protection scope of the present invention.
Claims (10)
1. a kind of Fe-series catalyst, it is characterised in that be made up of major catalyst and co-catalyst,
Major catalyst is pyridine imine iron complex, and its general structure is as follows：
,
In formula, X is halogen；R1For、Or；R2For-H ,-CH3、-CH2CH3Or phenyl；R3
For-H, alkyl, aryl or halogen；
Co-catalyst is MAO, and general structure is, wherein n is the natural number of 4-40；
The mol ratio of the ferro element in aluminium element and major catalyst in co-catalyst is 500:1.
2. Fe-series catalyst according to claim 1, it is characterised in that X is Br or Cl, R in pyridine imine iron complex2
For-H; R3For-H.
3. Fe-series catalyst according to claim 1, it is characterised in that pyridine imine iron complex structural formula is
、Or。
4. in the Fe-series catalyst any one of a kind of claim 1-3 major catalyst pyridine imine iron complex preparation
Method, it is characterised in that at room temperature, by pyridine imine ligand in dichloromethane solvent with the halide of iron with equimolar ratio
Reaction, through post processing, obtains final product.
5. application of the Fe-series catalyst any one of a kind of claim 1-3 in isoprene polymerization.
6. after application according to claim 5, it is characterised in that by co-catalyst, toluene and isoprene are separately added into,
Adding the dichloromethane solution of major catalyst carries out polymerisation so as to obtain polyisoprene.
7. application according to claim 6, it is characterised in that in monomer isoprene and Fe-series catalyst in major catalyst
The mol ratio of ferro element is 2500：1.
8. application according to claim 6, it is characterised in that the temperature of polymerisation is -25 ~ 25oC, polymerization time is 2
Hour.
9. the application according to any one of claim 5-8, it is characterised in that the polyisoprene number-average molecular weight for obtaining
For 6.1 × 104-28.2×104, molecular weight distribution 1.61-2.08.
10. the application according to any one of claim 5-8, it is characterised in that cis in the polyisoprene for obtaining-Isosorbide-5-Nitrae
Structure proportion scope is 62.7% ~ 86.7%, anti-form-1, and 4 structure proportion scopes are 2.8% ~ 8.2%, shared by 3,4 structures
Proportion is 6.7% ~ 34.5%.
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