CN108659055A - A kind of iron complex, preparation method and its application in isoprene polymerization based on flexible back bone - Google Patents
A kind of iron complex, preparation method and its application in isoprene polymerization based on flexible back bone Download PDFInfo
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Abstract
The invention discloses a kind of iron complex, preparation method and its application in isoprene polymerization based on flexible back bone, it is described based on the iron complex of flexible back bone as major catalyst, co-catalyst is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, methylaluminoxane or the methylaluminoxane of modification.Step is：By major catalyst, after solvent and co-catalyst addition, adds isoprene monomer and carry out polymerisation to obtain polyisoprene.Cis- Isosorbide-5-Nitrae structure proportion ranging from 29 48% in obtained isoprene rubber, 3,4 structure proportions ranging from 52 71%.And polymer molecular weight is high, narrow molecular weight distribution.Isoprene rubber preparation method provided by the invention can effectively improve the service efficiency and industrial application value of Fe-series catalyst.
Description
Technical field
The present invention relates to the field of chemical synthesis.
Background technology
Isoprene rubber not only has certain similar to natural rubber as one of superior synthetic rubber kind of comprehensive performance
Characteristic, also there are the advantages such as synthesis material derives from a wealth of sources, processing performance is good, played increasingly in China Synthetic Rubber Industry
Important role.Since Williams in 1860 isolates isoprene from natural rubber decomposition product, more and more sections
Scholar is dedicated to the research of isoprene natural man-made rubber.There are four types of diverse microcosmic structures for polyisoprene：Cis-1,4- is poly-
Isoprene；Trans-1,4- polyisoprene；3,4- polyisoprene and 1,2- polyisoprene.Because in polyisoprene
There are different structural units and structural unit connection type, so there is larger poor performance between different polyisoprene
It is different.For example, cis-1,4- polyisoprene have the microstructure as natural rubber, it can be as the replacement of natural rubber
Product；3,4- polyisoprene have larger side group, are generally used for the anti-slippery modifier of tire, shock resistant damping material etc..
Early in the 1960s, iron catalyst is just used for the catalytic polymerization of conjugated diene, for preparing dimerization
Object, trimer and a small amount of high polymer, but these all no progress in-depth studies.1970, Swift seminars report
The polymerization of three component catalyst systems catalysis isoprene：By at Fe (acac)3/AlEt3Middle addition containing n-donor ligand catalyzes and synthesizes
The polyisoprene of the cis-1,4 of same amount and 3,4 structures.But the catalytic polymerization need to carry out just having at -23 DEG C
The raising of greater activity, polymerization temperature can cause polymer yield to significantly reduce, this may be because of the catalyst activity generated
Center is unstable at high temperature or iron catalyst is inactivated by over reduction.2004, Zhang Xuequan seminars had studied Fe
(acac)3/Al(i-Bu)3/ diethyl phosphite ternary system is catalyzed isoprene polymerization.On this basis, which studies
Al (i-Bu) is substituted with MMAO3Iron as co-catalyst is catalyzed isoprene polymerization, can be with obtained 3,4 knots of higher activity
Structure polyisoprene.2012, Ritter projects were combined into iron/pyridine imine complex, were formed in conjunction with alkyl aluminum and boron salt
Ternary system is catalyzed isoprene polymerization, has higher activity and regioselectivity.Unlike iron catalytic polymerization before,
The polyisoprene structure that the catalyst system and catalyzing obtains can be adjusted based on Isosorbide-5-Nitrae structure by the variation of ligand structure
It is whole：Polyisoprene prepared by complex containing alkyl substituent is with trans-1, based on 4 structures, and matching containing aryl substituent
The polyisoprene of object preparation is closed based on cis-1,4 structures.On this basis, the happy seminar's designs of Chen Chang have synthesized a series of
Iron/pyridine alkyl imino and iron/pyridine aryl imine complex.Using MAO as co-catalyst, have studied containing different substituents
Influence of the ligand to reactivity and stereoselectivity.Different from the three-element catalytic system of the reports of Ritter before, which urges
The Isosorbide-5-Nitrae structure polyisoprene that change system obtains only has moderate yield (62-78%), and aryl substitution and alkyl substitution cooperation
Object influences catalytic selectivity little.
The activity and selectivity for the Fe-series catalyst catalysis isoprene polymerization reported at present is not high, also from industrial applications
There is prodigious gap.Therefore, the catalyst of synthesizing new is designed to realize iron catalysis isoprene high activity, highly-solid selectively
Controllable polymerization still have highly important research significance and realistic price.
Invention content
In order to solve polymer molecular weight wider distribution present in the above existing isoprene polymerization technology, aggregate into
This height and the problems such as can not carry out controllable polymerization to catalysis microstructure, this application provides a kind of novel iron catalysis
Agent.The pyridine benzyl imines/iron complex for using structure more flexible is as major catalyst, in industrialized co-catalyst MAO
Under the action of be catalyzed isoprene polymerization, polymerization activity is higher, and obtained molecular weight is higher, and molecular weight distribution is relatively narrow, passes through
The controllable of polyisoprene structure is realized to the regulation and control of major catalyst structure and reaction condition.
The present invention also provides the preparation methods of the pyridine imine/iron catalyst.
The preparation method of the iron complex：At room temperature, in methylene chloride, by '-imine pyridinyl ligand and protochloride
Iron, than reacting, iron complex is obtained after post-treated with equimolar.Post-processing operation is that vacuum drains dichloromethane, uses n-hexane
Washing three times, is dried under vacuum to constant weight.
The present invention also provides application of the iron catalyst in isoprene polymerization.
The present invention is achieved by the following technical solutions：
A kind of iron complex based on flexible back bone, structure is shown in formula I,
In formula, R be 4- is fluorine-based, 2,6- bis- is fluorine-based, 4- trifluoromethyls, 2- methyl, in 2,4,6- trimethyls or 4- methoxyl groups
One or two or more kinds, preferably R be 2,6- bis- it is fluorine-based, structural formula is formula III：
The preparation method of the iron complex based on flexible back bone, is included under the conditions of 25-60 DEG C, in tetrahydrofuran or
In dichloromethane, pyridine imine ligand is reacted with frerrous chloride with equimolar ratio, iron complex is obtained after post-treated.
The pyridine imine ligand general structure is：Concrete structure formula is in following structural formula
It is one or two or more kinds of：
It is described to be based on the present invention also provides the above-mentioned application based on the iron complex of flexible back bone in isoprene polymerization
For the iron complex of flexible back bone as major catalyst, co-catalyst is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, aluminium methyl
Oxygen alkane or the methylaluminoxane of modification；The general structure of methylaluminoxane (MAO) isWherein n is the nature of 4-40
Number；The molar ratio of the ferro element in aluminium element and major catalyst in co-catalyst is (10-500):1.
Step is：By major catalyst, after solvent and co-catalyst addition, adds isoprene monomer and carry out polymerisation
To obtain polyisoprene.
The polymerization solvent is toluene, paraxylene, n-hexane, hexamethylene, pentane, dichloromethane, tetrahydrochysene furan
It mutters, preferably toluene；The dosage of solvent is：The volume ratio of solvent and isoprene monomer is (1-10):1.
The polymeric reaction temperature is -30-50 DEG C, preferably 25 DEG C；
The polymerization reaction time is 10min-1h, preferably 10min.
The molar ratio of the isoprene monomer and major catalyst is (200-10000):1, preferably 2000:1；
The molar ratio of the ferro element in aluminium element and major catalyst in the co-catalyst is (10-500):1, preferably
100:1；
The preferred charging sequence of polymerisation charging sequence is major catalyst, solvent, co-catalyst, isoprene list
Body；
The polyisoprene number-average molecular weight of the preparation is 23.2 × 104-37.5×104, molecular weight distribution 1.8-
3.6。
The cis- Isosorbide-5-Nitrae structure proportion ranging from 29-48% of polyisoprene of the preparation, 3,4 structure proportions
Ranging from 52-71%.
Advantageous effect
(1) major catalyst in the Fe-series catalyst of the application is iron/benzyl '-imine pyridinyl complex, synthetic method letter
It is single, it is cheap；Co-catalyst is MAO, and the boron salt price relative to three components in background introduction is less expensive；
(2) Fe-series catalyst of the application can realize isoprene high activity, highly selective controllable polymerization, polymerization activity
Up to 107, obtained polyisoprene number-average molecular weight is 23.2 × 104-37.5×104, molecular weight distribution 1.8-3.6.
Description of the drawings
Fig. 1 is the ligand nucleus magnetic hydrogen spectrum that preparation example 1 obtains；
Fig. 2 is the ligand nuclear-magnetism carbon spectrum that preparation example 1 obtains；
Fig. 3 is the nucleus magnetic hydrogen spectrum of the polyisoprene obtained in example 3；
Fig. 4 is the nuclear-magnetism carbon spectrum of the polyisoprene obtained in example 3.
Case study on implementation
Preparation example 1
Pyridine imine iron complex shown in the present embodiment formula II：
100mL dry reaction bottles are added 4A molecular sieves and toast 30 minutes.Under argon atmosphere, dry dichloromethane is sequentially added
Alkane (40mL), 4- fluorin benzyl amines (1.2g, 9.3mmol) and pyridine-2-formaldehyde (1.0g, 9.3mmol).Reaction is stayed overnight at room temperature, TLC
Plate detection reaction aldehyde substrate reactions are complete.Filtering, is spin-dried for, is drained under vacuum, obtain yellow liquid (1.9g, yield：93%) it, ties
Structure formula is
25mL dry reaction pipes, sequentially add in glove box 15mL steam again dichloromethane, equimolar than anhydrous FeCl2
(100.0mg, 0.8mmol) and the pyridine imine ligand of above-mentioned preparation (169.0mg, 0.8mmol) stir 15h at room temperature.Reaction
After, vacuum drains dichloromethane, and 10mL drying n-hexanes are added and wash 3 times, vacuum is drained to constant weight, and 246mg purples are obtained
Solid (yield：83%).
Mass spectral analysis：C13H11ClFFeN2[M-Cl]+Theoretical value：304.9944；Measured value：304.9911.
Elemental analysis：C13H11Cl2FFeN2：Theoretical value：C, 45.79%；H, 3.25%；N, 8.22%；Measured value：C,
45.63%；H, 3.19%；N, 8.11%.
Preparation example 2
Pyridine imine iron complex shown in the present embodiment formula III：
100mL dry reaction bottles are added 4A molecular sieves and toast 30 minutes.Under argon atmosphere, dry dichloromethane is sequentially added
Alkane (40mL), 2,6- difluorobenzylamines (1.34g, 9.34mmol) and 2- pyridine carboxaldehydes (1.0g, 9.34mmol).It reacted at room temperature
Night, TLC plates detection reaction aldehyde substrate reactions are complete.Filtering, is spin-dried for, is drained under vacuum, obtain yellow solid (1.7g, yield：
79%), structural formula is
25mL dry reaction pipes, sequentially add in glove box 15mL steam again dichloromethane, equimolar than anhydrous FeCl2
(100.0mg, 0.8mmol) and the pyridine imine ligand of above-mentioned preparation (183.0mg, 0.8mmol) stir 15h at room temperature.Reaction
After, vacuum drains dichloromethane, and 10mL drying n-hexanes are added and wash 3 times, vacuum is drained to constant weight, and 241mg purples are obtained
Solid (yield：85%).
Mass spectral analysis：C13H10ClF2FeN2[M-Cl]+Theoretical value：322.9850；Measured value：322.9813.
Elemental analysis：C13H10Cl2F2FeN2：Theoretical value：C, 43.50%；H, 2.81%；N, 7.80%；Measured value：C,
43.41%；H, 2.84%；N, 2.48%.
Preparation example 3
Pyridine imine iron complex shown in the present embodiment formula IV：
100mL dry reaction bottles are added 4A molecular sieves and toast 30 minutes.Under argon atmosphere, dry dichloromethane is sequentially added
Alkane (60mL), 4- trifluoromethyl benzylamines (2.5g, 14.0mmol) and pyridine-2-formaldehyde (1.5g, 14.0mmol).It reacts at room temperature
Overnight, TLC plates detection reaction aldehyde substrate reactions are complete.Filtering, is spin-dried for, is drained under vacuum, obtain yellow liquid (3.3g, yield：
90%), structural formula is
25mL dry reaction pipes, sequentially add in glove box 15mL steam again dichloromethane, equimolar than anhydrous FeCl2
(100.0mg, 0.8mmol) and the pyridine imine ligand of above-mentioned preparation (208.5mg, 0.8mmol) stir 15h at room temperature.Reaction
After, vacuum drains dichloromethane, and 10mL drying n-hexanes are added and wash 3 times, vacuum is drained to constant weight, and 240mg purples are obtained
Solid (yield：78%).
Mass spectral analysis：C14H11ClF3FeN2[M-Cl]+Theoretical value：354.9912；Measured value：354.9933.
Elemental analysis：C14H11Cl2F3FeN2：Theoretical value：C, 43.01%；H, 2.84%；N, 7.16%；Measured value：C,
42.92%；H, 2.91%；N, 7.22%.
Preparation example 4
Pyridine imine iron complex shown in the present embodiment formula V：
100mL dry reaction bottles are added 4A molecular sieves and toast 30 minutes.Under argon atmosphere, dry dichloromethane is sequentially added
Alkane (60mL), 2- methylbenzylamines (1.1g, 9.3mmol) and pyridine-2-formaldehyde (1.0g, 9.3mmol).Reaction is stayed overnight at room temperature,
TLC plates detection reaction aldehyde substrate reactions are complete.Filtering, is spin-dried for, is drained under vacuum, obtain light yellow liquid (3.3g, yield：
90%), structural formula is
25mL dry reaction pipes, sequentially add in glove box 15mL steam again dichloromethane, equimolar than anhydrous FeCl2
(100.0mg, 0.8mmol) and the pyridine imine ligand of above-mentioned preparation (165.9mg, 0.8mmol) stir 15h at room temperature.Reaction
After, vacuum drains dichloromethane, and 10mL drying n-hexanes are added and wash 3 times, vacuum is drained to constant weight, and 160mg purples are obtained
Solid (yield：60%).
Mass spectral analysis：C14H14Cl2FeN2[M-Cl]+Theoretical value：301.0195；Measured value：301.0178.
Elemental analysis：C14H14Cl2FeN2：Theoretical value：C, 49.89%；H, 4.19%；N, 8.31%；Measured value：C,
49.72%；H, 3.83%；N, 7.20%.
Preparation example 5
Pyridine imine iron complex shown in the present embodiment formula VI：
100mL dry reaction bottles are added 4A molecular sieves and toast 30 minutes.Under argon atmosphere, dry dichloromethane is sequentially added
Alkane (60mL), 2,4,6- trimethyl benzylamines (1.4g, 9.4mmol) and pyridine-2-formaldehyde (1.0g, 9.3mmol).It reacts at room temperature
Overnight, TLC plates detection reaction aldehyde substrate reactions are complete.Filtering, is spin-dried for, is drained under vacuum, obtain yellow solid (1.9g, yield：
85%), structural formula is
25mL dry reaction pipes, sequentially add in glove box 15mL steam again dichloromethane, equimolar than anhydrous FeCl2
(50.0mg, 0.4mmol) and the pyridine imine ligand of above-mentioned preparation (94.0mg, 0.4mmol) stir 12h at room temperature.Reaction knot
Shu Hou, vacuum drain dichloromethane, and 10mL drying n-hexanes are added and wash 3 times, vacuum is drained to constant weight, and it is solid to obtain 128mg purples
Body (yield：89%).
Mass spectral analysis：C16H18ClFeN2[M-Cl]+Theoretical value：329.0508；Measured value：329.0527.
Elemental analysis：C16H18Cl2FeN2：Theoretical value：C, 52.64%；H, 4.97%；N, 7.67%；Measured value：C,
52.49%；H, 5.06%；N, 7.85%.
Preparation example 6
Pyridine imine iron complex shown in the present embodiment formula VII：
100mL dry reaction bottles are added 4A molecular sieves and toast 30 minutes.Under argon atmosphere, dry dichloromethane is sequentially added
Alkane (60mL), 2,4,6- trimethyl benzylamines (1.3g, 9.4mmol) and pyridine-2-formaldehyde (1.0g, 9.3mmol).It reacts at room temperature
Overnight, TLC plates detection reaction aldehyde substrate reactions are complete.Filtering, is spin-dried for, is drained under vacuum, obtain yellow liquid (2.0g, yield：
93%), structural formula is
25mL dry reaction pipes, sequentially add in glove box 15mL steam again dichloromethane, equimolar than anhydrous FeCl2
(100mg, 0.79mmol) and the pyridine imine ligand of above-mentioned preparation (178.5mg, 0.8mmol) stir for 24 hours at room temperature.Reaction knot
Shu Hou, vacuum drain dichloromethane, and 10mL drying n-hexanes are added and wash 3 times, vacuum is drained to constant weight, and it is solid to obtain 220mg purples
Body (yield：79%).
Mass spectral analysis：C14H14ClFeN2O[M-Cl]+Theoretical value：317.0144；Measured value：317.0123.
Elemental analysis：C14H14Cl2FeN2O：Theoretical value：C, 47.63%；H, 4.00%；N, 7.94%；Measured value：C,
47.59%；H, 3.85%；N, 7.89%.
Embodiment 1
25mL dry reaction pipes, are transferred in glove box, and major catalyst 3.4mg (10 μ shown in load weighted Formula II are added
Mol), it is transferred to outside glove box, dry toluene 5ml is added under argon atmosphere, methylaluminoxane 3.33mL (1.5M) is added
Isoprene monomer 2ml (20mmol), reacts 10min at room temperature, with the methanol dilute hydrochloric acid (1 of 20ml:50, V/V) solution is whole
It only reacts, filters, washed with a large amount of ethyl alcohol, vacuum is drained to constant weight, yield 100%, number-average molecular weight 243715 at room temperature,
Molecular weight distribution is that 2.5, cis-1,4 structural contents are 48%, and 3,4 structural contents are 52%.
Embodiment 2
25mL dry reaction pipes, are transferred in glove box, and major catalyst 3.6mg (10 μ shown in load weighted formula III are added
Mol), it is transferred to outside glove box, dry toluene 5ml is added under argon atmosphere, methylaluminoxane 3.33mL (1.5M) is added
Isoprene monomer 2ml (20mmol), reacts 10min at room temperature, with the methanol dilute hydrochloric acid (1 of 20ml:50, V/V) solution is whole
It only reacts, filters, washed with a large amount of ethyl alcohol, vacuum is drained to constant weight, yield 100%, number-average molecular weight 375197 at room temperature,
Molecular weight distribution is that 1.8, cis-1,4 structural contents are 44%, and 3,4 structural contents are 56%.
Embodiment 3
25mL dry reaction pipes, are transferred in glove box, and major catalyst 3.9mg (10 μ shown in load weighted formula IV are added
Mol), it is transferred to outside glove box, dry toluene 5ml is added under argon atmosphere, methylaluminoxane 3.33mL (1.5M) is added
Isoprene monomer 2ml (20mmol), reacts 10min at room temperature, with the methanol dilute hydrochloric acid (1 of 20ml:50, V/V) solution is whole
It only reacts, filters, washed with a large amount of ethyl alcohol, vacuum is drained to constant weight, yield 100%, number-average molecular weight 281684 at room temperature,
Molecular weight distribution is that 3.6, cis-1,4 structural contents are 43%, and 3,4 structural contents are 57%.
Embodiment 4
25mL dry reaction pipes, are transferred in glove box, and major catalyst 3.4mg (10 μ shown in load weighted Formula V are added
Mol), it is transferred to outside glove box, dry toluene 5ml is added under argon atmosphere, methylaluminoxane 3.33mL (1.5M) is added
Isoprene monomer 2ml (20mmol), reacts 10min at room temperature, with the methanol dilute hydrochloric acid (1 of 20ml:50, V/V) solution is whole
It only reacts, filters, washed with a large amount of ethyl alcohol, vacuum is drained to constant weight, yield 100%, number-average molecular weight 329983 at room temperature,
Molecular weight distribution is that 2.0, cis-1,4 structural contents are 33%, and 3,4 structural contents are 67%.
Embodiment 5
25mL dry reaction pipes, are transferred in glove box, and major catalyst 3.6mg (10 μ shown in load weighted Formula IV are added
Mol), it is transferred to outside glove box, dry toluene 5ml is added under argon atmosphere, methylaluminoxane 3.33mL (1.5M) is added
Isoprene monomer 2ml (20mmol), reacts 10min at room temperature, with the methanol dilute hydrochloric acid (1 of 20ml:50, V/V) solution is whole
It only reacts, filters, washed with a large amount of ethyl alcohol, vacuum is drained to constant weight, yield 100%, number-average molecular weight 351581 at room temperature,
Molecular weight distribution is that 2.4, cis-1,4 structural contents are 29%, and 3,4 structural contents are 71%.
Embodiment 6
25mL dry reaction pipes, are transferred in glove box, and major catalyst 3.5mg (10 μ shown in load weighted Formula VII are added
Mol), it is transferred to outside glove box, dry toluene 2ml is added under argon atmosphere, methylaluminoxane 3.33mL (1.5M) is added
Isoprene monomer 2ml (20mmol), reacts 10min at room temperature, with the methanol dilute hydrochloric acid (1 of 20ml:50, V/V) solution is whole
It only reacts, filters, washed with a large amount of ethyl alcohol, vacuum is drained to constant weight, yield 100%, number-average molecular weight 256870 at room temperature,
Molecular weight distribution is that 2.0, cis-1,4 structural contents are 46%, and 3,4 structural contents are 54%.
Embodiment 7
The polymerization of isoprene is carried out using 2 method of embodiment, unlike, use 5.0mL triethyl aluminums
(1.0M) reacts 1h as co-catalyst, is precipitated without solid after being quenched.
Embodiment 8
The polymerization of isoprene is carried out using 2 method of embodiment, unlike, use 5.0mL triisobutyl aluminiums
(1.0M) reacts 1h as co-catalyst, is precipitated without solid after being quenched.
Embodiment 9
The polymerization of isoprene is carried out using 2 method of embodiment, unlike, use 5.0mL aluminium diethyl monochlorides
(1.0M) reacts 1h as co-catalyst, is precipitated without solid after being quenched.
Embodiment 10
The polymerization of isoprene is carried out using 2 method of embodiment, unlike, use one aluminium ethide of 5.0mL dichloros
(1.0M) reacts 1h as co-catalyst, and a large amount of white solids are precipitated after being quenched, and is cross-linking by-products.
Embodiment 11
The polymerization of isoprene is carried out using 2 method of embodiment, unlike, use 0.67mL methylaluminoxane
(1.5M) reacts 10min as co-catalyst, a large amount of white solids, yield 100% is precipitated after being quenched, number-average molecular weight is
331563,1.9, cis-1,4 structural content of molecular weight distribution is 45%, and 3,4 structural contents are 55%.
Embodiment 12
The polymerization of isoprene is carried out using 2 method of embodiment, unlike, use 0.33mL methylaluminoxane
(1.5M) reacts 10min as co-catalyst, a large amount of white solids, yield 99% is precipitated after being quenched, number-average molecular weight is
236954,2.0, cis-1,4 structural content of molecular weight distribution is 44%, and 3,4 structural contents are 56%.
Embodiment 13
The polymerization of isoprene is carried out using 2 method of embodiment, unlike, use 0.067mL methylaluminoxane
(1.5M) reacts 10min as co-catalyst, a large amount of white solids, yield 80% is precipitated after being quenched, number-average molecular weight is
267520,2.0, cis-1,4 structural content of molecular weight distribution is 44%, and 3,4 structural contents are 56%.
Embodiment 14
The polymerization of isoprene is carried out using 2 method of embodiment, unlike, use 0.033mL methylaluminoxane
(1.5M) reacts 10min as co-catalyst, is precipitated without solid after being quenched.
Embodiment 15
The polymerization of isoprene is carried out using 13 method of embodiment, unlike, catalytic polymerization 30min quenches
A large amount of white solids, yield 91%, number-average molecular weight 199631,2.2, cis-1,4 knot of molecular weight distribution are precipitated after going out
Structure content is 44%, and 3,4 structural contents are 56%.
Embodiment 16
The polymerization of isoprene is carried out using 13 method of embodiment, unlike, catalytic polymerization 1h, after being quenched
It is precipitated a large amount of white solids, yield 100%, number-average molecular weight 115862,2.3, cis-1,4 structure of molecular weight distribution contains
Amount is 45%, and 3,4 structural contents are 55%.
Embodiment 17
The polymerization of isoprene is carried out using 11 method of embodiment, unlike, charging sequence is anti-raw to be changed：25mL
Dry reaction pipe, is transferred in glove box, and major catalyst 3.4mg shown in load weighted Formula II (10 μm of ol) is added, is transferred to hand
Outside casing, dry toluene 5ml is added under argon atmosphere, isoprene monomer 2ml (20mmol) adds methylaluminoxane
0.67mL(1.5M).A large amount of white solids, yield 100%, number-average molecular weight 95411, molecular weight distribution are precipitated after being quenched
Be 5.6, cis-1,4 structural contents be 38%, 3,4 structural contents be 62%.
Embodiment 18
The polymerization of isoprene is carried out using 11 method of embodiment, unlike, charging sequence is anti-raw to be changed：25ml
Dry toluene 5ml, isoprene 2ml (20mmol), methylaluminoxane 0.67mL is added in dry reaction pipe under argon atmosphere
(1.5M) is eventually adding dichloromethane (1ml) solution of catalyst (R is 4- fluorine) 3.4mg (10 μm of ol).It is precipitated after being quenched a large amount of
White solid, yield 100%, number-average molecular weight 256430,2.6, cis-1,4 structural content of molecular weight distribution are
48%, 3,4 structural contents are 52%.
Embodiment 19
The polymerization of isoprene is carried out using 11 method of embodiment, unlike, charging sequence is anti-raw to be changed, and is used
" one kettle way " prepares polyisoprene：Frerrous chloride, ligand and dry toluene is added in 25ml dry reaction pipes under argon atmosphere
5ml reacts 30min at room temperature, sequentially adds methylaluminoxane 0.67mL (1.5M), isoprene 2ml (20mmol), reaction
10min.It is precipitated a large amount of white solids after being quenched, yield 100%, number-average molecular weight 314498, molecular weight distribution 2.0,
Cis-1,4 structural contents are 43%, and 3,4 structural contents are 57%.
Embodiment 20
250mL dry reaction pipes, are transferred in glove box, and major catalyst 14.4mg (40 shown in load weighted formula III is added
μm ol), it is transferred to outside glove box, dry toluene 50ml, methylaluminoxane 13.3mL (1.5M) is added under argon atmosphere, then add
Enter isoprene 20ml (200mmol), react 10min at room temperature, with the methanol dilute hydrochloric acid (50 of 200ml:1) solution terminates anti-
It answers, filters, washed with a large amount of ethyl alcohol, vacuum is drained to constant weight, yield 90%, number-average molecular weight 321660, molecule at room temperature
It is 45% that amount, which is distributed as 2.0, cis-1,4 structural contents, and 3,4 structural contents are 55%.
Claims (10)
1. a kind of iron complex based on flexible back bone, which is characterized in that the structure of the iron complex is shown in formula I,
In formula, R be 4- is fluorine-based, 2,6- bis- is fluorine-based, 4- trifluoromethyls, 2- methyl, one in 2,4,6- trimethyls or 4- methoxyl groups
Kind or two kinds or more.
2. iron complex according to claim 1, which is characterized in that the iron complex structure based on flexible back bone is
In one or two or more kinds.
3. according to the preparation method of the iron complex based on flexible back bone described in claim any one of 1-2, which is characterized in that
The method includes under the conditions of 25-60 DEG C, in tetrahydrofuran or dichloromethane, by pyridine imine ligand and frerrous chloride with
Equimolar obtains iron complex than reaction after post-treated.
4. method according to claim 3, which is characterized in that the pyridine imine ligand structural formula is in following structural formula
It is one or two or more kinds of：
5. a kind of application as claimed in claim 1 or 2 based on the iron complex of flexible back bone in isoprene polymerization, special
Sign is, it is described based on the iron complex of flexible back bone as major catalyst, co-catalyst is trimethyl aluminium, triethyl aluminum, three
Aluminium isobutyl, methylaluminoxane or the methylaluminoxane of modification；The general structure of methylaluminoxane (MAO) isIts
Middle n is the natural number of 4-40；The molar ratio of the ferro element in aluminium element and major catalyst in co-catalyst is (10-500):1.
6. application according to claim 5, which is characterized in that step is：By major catalyst, solvent and co-catalyst are added
Afterwards, it adds isoprene monomer and carries out polymerisation to obtain polyisoprene.
7. application according to claim 6, which is characterized in that the solvent is toluene, paraxylene, n-hexane, hexamethylene
One or two or more kinds in alkane, pentane, dichloromethane, tetrahydrofuran；Monomer isoprene and ferro element in major catalyst
Molar ratio is (200-10000):1.
8. application according to claim 6, which is characterized in that the temperature of polymerisation is -30-50 DEG C.
9. application according to claim 6, which is characterized in that polymerization time 10min-1h.
10. according to the application described in any one of claim 5-8, which is characterized in that the obtained equal molecule of polyisoprene number
Amount is 23.2 × 104-37.5×104, molecular weight distribution 1.8-3.6；Obtained polyisoprene cis-1,4 structure institute accounting
Example ranging from 29-48%, 3,4 structure proportion ranging from 52-71%.
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| CN111233938A (en) * | 2020-03-27 | 2020-06-05 | 中国科学院青岛生物能源与过程研究所 | Pyrimidineacetylacetone ferrous complex, preparation method thereof and method for catalyzing polymerization of conjugated diene by using same |
| CN114736245A (en) * | 2022-04-20 | 2022-07-12 | 中国科学院青岛生物能源与过程研究所 | Pyridine-2-oxime-iron complex, preparation method thereof and application thereof in preparation of conjugated diene rubber |
| WO2022183467A1 (en) * | 2021-03-05 | 2022-09-09 | 中国科学院青岛生物能源与过程研究所 | Heteroaromatic ring tridentate pyridine imine iron complex, preparation method therefor, and application thereof in catalysis of conjugated diene polymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012109343A2 (en) * | 2011-02-08 | 2012-08-16 | President And Fellows Of Harvard College | Iron complexes and methods for polymerization |
| CN106632764A (en) * | 2016-10-17 | 2017-05-10 | 曲阜师范大学 | Iron-based catalyst, preparation method of iron-based catalyst, and application of iron-based catalyst in isoprene polymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012109343A2 (en) * | 2011-02-08 | 2012-08-16 | President And Fellows Of Harvard College | Iron complexes and methods for polymerization |
| CN106632764A (en) * | 2016-10-17 | 2017-05-10 | 曲阜师范大学 | Iron-based catalyst, preparation method of iron-based catalyst, and application of iron-based catalyst in isoprene polymerization |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111233938A (en) * | 2020-03-27 | 2020-06-05 | 中国科学院青岛生物能源与过程研究所 | Pyrimidineacetylacetone ferrous complex, preparation method thereof and method for catalyzing polymerization of conjugated diene by using same |
| CN111233938B (en) * | 2020-03-27 | 2023-02-17 | 中国科学院青岛生物能源与过程研究所 | Pyrimidineacetylacetone ferrous complex, preparation method thereof and method for catalyzing polymerization of conjugated diene by using same |
| WO2022183467A1 (en) * | 2021-03-05 | 2022-09-09 | 中国科学院青岛生物能源与过程研究所 | Heteroaromatic ring tridentate pyridine imine iron complex, preparation method therefor, and application thereof in catalysis of conjugated diene polymerization |
| CN114736245A (en) * | 2022-04-20 | 2022-07-12 | 中国科学院青岛生物能源与过程研究所 | Pyridine-2-oxime-iron complex, preparation method thereof and application thereof in preparation of conjugated diene rubber |
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