CN109134730A - A kind of aryl substituted pyridine amine Fe-series catalyst and the preparation method and application thereof - Google Patents
A kind of aryl substituted pyridine amine Fe-series catalyst and the preparation method and application thereof Download PDFInfo
- Publication number
- CN109134730A CN109134730A CN201810864108.3A CN201810864108A CN109134730A CN 109134730 A CN109134730 A CN 109134730A CN 201810864108 A CN201810864108 A CN 201810864108A CN 109134730 A CN109134730 A CN 109134730A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- reaction
- pyridine amine
- isoprene
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers 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
- C08F136/04—Homopolymers 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
- C08F136/08—Isoprene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a kind of aryl substituted pyridine amine Fe-series catalysts and the preparation method and application thereof, it is related to conjugated diene catalysis polymerization technology field, the Fe-series catalyst, it is made of major catalyst and co-catalyst, major catalyst is aryl substituted pyridine amine iron complex, co-catalyst is methylaluminoxane or alkyl aluminum, and co-catalyst and major catalyst molar ratio are 100:1-2000:1.Above-mentioned iron catalyst system shows as greater activity in isoprene polymerization, obtained polymer molecular weight is high, molecular weight distribution is relatively narrow, the microstructure of polymer can be regulated and controled by adjusting major catalyst structure simultaneously, meanwhile the activity of reaction depends on the major catalyst and variety classes co-catalyst of different substituents.
Description
Technical field
The present invention relates to conjugated diene catalytic polymerization fields, and in particular to a kind of pyridine amine Fe-series catalyst further relates to
The preparation method of catalyst and the application in isoprene polymerization.
Background technique
In recent years, environmental-friendly late transition metal catalysis in olefine polymerization causes scientists more and more to be paid close attention to.Iron
Series catalysts because of its environment friendly, economy, biocompatibility and have preferable tolerance to polar monomer, in isoamyl
Also extensive concern is obtained in diene polymerization.The containing n-donor ligand of the isoprene polymerization of iron catalyst catalysis at present is mainly sp2- N,
sp2- N pyridine imine class, but that there are catalyst structures or activated centre is indefinite, active low, poor selectivity, conjunction for the system
It is low at polymer molecular weight.
Summary of the invention
To solve the above problems, the present invention provides a kind of aryl substituted pyridine amine Fe-series catalyst and preparation method thereof
With application.
A kind of aryl substituted pyridine amine Fe-series catalyst, it is characterised in that: be made of major catalyst and co-catalyst, main reminder
Agent is pyridine amine iron complex, and general structural Formula isWherein, R1For phenyl, substituted-phenyl or substitution
Hetero-aromatic ring；R2For H, methyl, ethyl or phenyl；R3For hydrogen, alkyl (is not limited to methyl, ethyl etc.), aryl (be not limited to phenyl, its
Its polyaromatic etc.) or halogen (Br, Cl etc.)；Co-catalyst is methylaluminoxane (MAO) or alkyl aluminum, the methyl alumina
Alkyl structure general formula isWherein n is the natural number of 4-40, and the alkyl aluminum is trimethyl aluminium, and triethyl aluminum, three is different
One of butyl aluminium；The molar ratio of the ferro element in aluminium element and major catalyst in co-catalyst is (100-2000): 1,
Preferred molar ratio is 500:1.Such system has high catalytic activity when being catalyzed isoprene polymerization reaction, and is polymerize
The microcosmic microstructure of object is mainly based on trans- 1,4 structure.
The pyridine amine iron complex, preferably R1For phenyl, 2,6- diisopropyl phenyls, 2,6- bis- (benzhydryl) benzene
Base, 4- trifluoromethyl, 2,4,6- trifluorophenyls, 4- methoxyphenyl；R2For H, R3For H, structural formula is in following structural formula
One kind:
The present invention also provides the preparation methods of above-mentioned pyridine amine iron complex: in anhydrous DCM, by pyridine amine ligand
With anhydrous FeCl2With molar ratio 1:1 mixing, it is stirred to react 24-48h at room temperature, after post treatment, is finally dried to obtain pyridine amine
Iron complex.
The post-processing, specifically: it is filtered under argon atmosphere, collects filter residue or filtrate, vacuum are drained, wash 2- with n-hexane
5 times (being achromaticity and clarification to filtrate).The drying is drained for vacuum.
The DCM dosage is so that the concentration of pyridine amine ligand is 0.1mol/L.
The pyridine amine ligand structural formula is one of following structural formula:
The present invention also provides application of the above-mentioned catalyst in isoprene polymerization: under the conditions of anhydrous and oxygen-free, to reaction
Pyridine amine iron complex, isoprene monomer, co-catalyst and solvent are added in device and forms reaction system, then stirring occurs poly-
Reaction is closed, quencher is added after reaction, twice with ethanol washing, separating-purifying obtains polyisoprene product.
The solvent is one of toluene, pentane or hexane or two kinds or more, preferably toluene, and makes isoprene
Concentration is 4mol/L.
In reaction system, the molar ratio of ferro element is (1000- in major catalyst in monomer isoprene and Fe-series catalyst
5000): 1, preferred molar ratio 2500:1.
The temperature of the polymerization reaction is 0 DEG C -50 DEG C, polymerization time 1-4h.Preferable reaction temperature is 25 DEG C, preferably instead
It is 2h between seasonable.
It further include dealkylating reagent in reaction system, the dealkylating reagent is B (C6F5)3, [Ph3C][B
(C6F5)4],[PhNMe2H][B(C6F5)4] one kind；Boron element and ferro element molar ratio in major catalyst in dealkylating reagent
For (1-10): 1.Preferred molar ratio is 1:1.
The quencher is methanolic HCl solution, and wherein the volume ratio of methanol and hydrochloric acid ratio is 50:1；Dosage is described molten
2 times of agent volume；Age resister can also be added after reaction, the age resister is that mass ratio is the tertiary fourth of 1%2,6- bis-
The ethanol solution of base -4- methylphenol, dosage are the 20% of the solvent volume.
In above-mentioned polymerization reaction, influence of the charging sequence to reactivity and selectivity.Charging sequence can be with are as follows:
(1) co-catalyst, solvent after isoprene sequentially adds, add major catalyst and carry out polymerization reaction to obtain
To polyisoprene；
Or (2) co-catalyst, solvent, after major catalyst sequentially adds, add isoprene carry out polymerization reaction from
And obtain polyisoprene.
Or (3) major catalyst, toluene, after isoprene sequentially adds, add co-catalyst carry out polymerization reaction from
And obtain polyisoprene.
The invention patent the utility model has the advantages that
1, the iron catalyst system of the application is that the first pyridine arylamine iron complex is catalyzed isoprene polymerization, main catalytic preparation
It is simple and easy to get, it is at low cost；Isoprene polymerization reaction can both carry out in two components of methylaluminoxane, can also be in alkyl
It is carried out in three groups that aluminium and alkylation removal reagent form.
2, it is entirely catalyzed isoprene polymerization system reactivity all with higher and the microstructure of polymer is main
For cis-1,4.0%-80% shared by cis-1 in obtained polyisoprene, 4- structure, trans-1,4- structure account for 0-30%,
20%-60% shared by 3,4- structure
3, the Fe-series catalyst of the application is to the industrialization isoprene and pure isoprene of reagent tolerance with higher,
For two components systems without using expensive alkylation removal reagent, cost is lower, has good industrial value.
Specific embodiment
Invention is further explained combined with specific embodiments below:
One, major catalyst pyridine imine iron complex is prepared
Embodiment 1
Pyridine imine iron complex shown in the present embodiment preparation formula (A):
25mL Schlenk reaction tube, which is taken out, roasting to be sequentially added 15mL three times, in glove box and steams methylene chloride, equimolar ratio again
Anhydrous FeCl2The pyridine imine ligand (1.5mmol) (structural formula LA) replaced with isopropyl, is stirred for 24 hours at room temperature.Reaction knot
Shu Hou, vacuum drain methylene chloride, and addition 10mL steams n-hexane again and washes 2 times (filtrate is achromaticity and clarification), and vacuum is drained to constant weight,
Greyish white solid is obtained, structural formula:
Mass spectral analysis: C12H12Cl2FeN2:[M-Cl]+: theoretical value: 275.0033；Measured value: 275.0042.
Elemental analysis: C12H12Cl2FeN2: theoretical value: C, 46.35；H,3.89；N,9.01；Measured value: C, 46.41%；H,
3.85%；N, 8.98%.
Embodiment 2
Pyridine imine iron complex shown in formula prepared by the present embodiment (B), preparation process are specific as follows:
25mL Schlenk reaction tube, which is taken out, roasting to be sequentially added 15mL three times, in glove box and steams methylene chloride, equimolar ratio again
Anhydrous FeCl2The pyridine imine ligand (1.5mmol) (structural formula LB) replaced with tert-butyl, is stirred for 24 hours at room temperature.Reaction knot
Shu Hou, vacuum drain methylene chloride, and addition 10mL steams n-hexane again and washes 2 times (filtrate is achromaticity and clarification), and vacuum is drained to constant weight,
Pale blue solid is obtained, structural formula:
Mass spectral analysis: C18H24Cl2FeN2[M-Cl]+: theoretical value: 359.0972；Measured value: 359.0968.
Elemental analysis: C18H24Cl2FeN2: theoretical value: C, 54.71；H,6.12；N,7.09；Measured value: C, 54.68%；H,
6.09%；N, 7.13%.
Embodiment 3
Pyridine imine iron complex shown in formula prepared by the present embodiment (C), preparation process are specific as follows:
10mL Schlenk reaction tube, which is taken out, roasting to be sequentially added 15mL three times, in glove box and steams methylene chloride, equimolar ratio again
Anhydrous FeCl2The pyridine imine ligand (1.5mmol) (structural formula LC) replaced with cyclohexyl, stirs 48h at room temperature.Reaction knot
Shu Hou, vacuum drain methylene chloride, and addition 10mL steams n-hexane again and washes 2 times (filtrate is achromaticity and clarification), and vacuum is drained to constant weight,
Light red solid is obtained, structural formula:
Mass spectral analysis: C38H32Cl2FeN2[M-Cl]+: theoretical value: 607.1598；Measured value: 607.1601.
Elemental analysis: C38H32Cl2FeN2: theoretical value: C, 70.93；H,5.01；N,4.35；Measured value: C, 71.01%；H,
4.98%；N, 4.30%.
Embodiment 4
Pyridine imine iron complex shown in formula prepared by the present embodiment (D), preparation process are specific as follows:
10mL Schlenk reaction tube, which is taken out, roasting to be sequentially added 15mL three times, in glove box and steams methylene chloride, equimolar ratio again
Anhydrous FeCl2The pyridine imine ligand (structural formula LD) (1.5mmol) replaced with cyclohexyl, stirs 48h at room temperature.Reaction knot
Shu Hou, vacuum drain methylene chloride, and addition 10mL steams n-hexane again and washes 2 times (filtrate is achromaticity and clarification), and vacuum is drained to constant weight,
Light yellow solid is obtained, structural formula:
Mass spectral analysis: C13H11Cl2F3FeN2[M-Cl]+: theoretical value: 342.9907；Measured value: 342.9905.
Elemental analysis: C13H11Cl2F3FeN2: theoretical value: C, 41.20；H,2.93；N, 7.39 measured values: C, 41.18%；
H, 2.95%；N, 7.41%.
Embodiment 5
Pyridine imine iron complex shown in formula prepared by the present embodiment (E), preparation process are specific as follows:
10mL Schlenk reaction tube, which is taken out, roasting to be sequentially added 15mL three times, in glove box and steams methylene chloride, equimolar ratio again
Anhydrous FeCl2The pyridine imine ligand (1.5mmol) (structural formula LE) replaced with cyclohexyl, stirs 48h at room temperature.Reaction knot
Shu Hou, vacuum drain methylene chloride, and addition 10mL steams n-hexane again and washes 2 times (filtrate is achromaticity and clarification), and vacuum is drained to constant weight,
Obtain brown solid structural formula:
Mass spectral analysis: C12H9Cl2F3FeN2[M-Cl]+: theoretical value: 328.9750；Measured value: 328.9755.
Elemental analysis: C12H9Cl2F3FeN2: theoretical value: C, 39.49；H,2.49；N,7.68；Measured value: C, 39.51%；
H, 2.51%；N, 7.71%.
Embodiment 6
Pyridine imine iron complex shown in formula prepared by the present embodiment (F), preparation process are specific as follows:
10mL Schlenk reaction tube, which is taken out, roasting to be sequentially added 15mL three times, in glove box and steams methylene chloride, equimolar ratio again
Anhydrous FeCl2The pyridine imine ligand (1.5mmol) (structural formula LF) replaced with cyclohexyl, stirs 48h at room temperature.Reaction knot
Shu Hou, vacuum drain methylene chloride, and addition 10mL steams n-hexane again and washes 2 times (filtrate is achromaticity and clarification), and vacuum is drained to constant weight,
Light yellow solid is obtained, structural formula:
Mass spectral analysis: C13H14Cl2FeN2O[M-Cl]+: theoretical value: 305.0139；Measured value: 305.0142.
Elemental analysis: C13H14Cl2FeN2O: theoretical value: C, 45.79；H,4.14；N,8.21；Measured value: C, 45.82%；
H, 4.09%；N, 8.16%.
Isoprene polymerization reaction
In catalytic polymerization, major catalyst can be individually added into, and can also be added in the form of its dichloromethane solution
Enter.
Embodiment 7
It under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially adds dry toluene 5mL, trimethyl is added
Aluminium (4mmol), isoprene (2mL, 20.0mmol), the 1mL for the catalyst (2.48mg, 10 μm of ol) that embodiment 1 is prepared
Dichloromethane solution polymerize 2h at 25 DEG C, reacts methanolic HCl solution (MeOH/HCl=50/1) quenching reaction for using 10mL,
Polymer is not obtained.
Embodiment 8
It under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially adds dry toluene 5mL, triethyl group is added
Aluminium (4mmol), isoprene (2mL, 20.0mmol), the 1mL bis- for the catalyst (2.48mg, 8 μm of ol) that embodiment 1 is prepared
Chloromethanes solution polymerize 2h at 25 DEG C, reacts methanolic HCl solution (MeOH/HCl=50/1) quenching reaction for using 10mL, not
Obtain polymer.
Embodiment 9
It under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially adds dry toluene 5mL, a chlorine two is added
Aluminium ethide (4mmol), isoprene (2mL, 20.0mmol), the catalyst (2.48mg, 8 μm of ol) that embodiment 1 is prepared
1mL dichloromethane solution, polymerize 2h at 25 DEG C, and reaction is quenched instead with the methanolic HCl solution (MeOH/HCl=50/1) of 10mL
It answers, does not obtain polymer.
Embodiment 10
It under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially adds dry toluene 5mL, two chloroethenes are added
Base aluminium (4mmol), isoprene (2mL, 20.0mmol), the 1mL for the catalyst (2.48mg, 8 μm of ol) that embodiment 1 is prepared
Dichloromethane solution polymerize 2h at 25 DEG C, reacts methanolic HCl solution (MeOH/HCl=50/1) quenching reaction for using 10mL,
Twice with ethanol washing, elastomer polymer is obtained.Yield > 99%, polymer are mostly cationic polymerization cross-linking products.
Embodiment 11
Under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially add dry toluene 5mL, methylaluminoxane
(4mmol), isoprene (2mL, 20.0mmol), the 1mL dichloro for the catalyst (2.48mg, 8 μm of ol) that embodiment 1 is prepared
Dichloromethane, polymerize 2h at 25 DEG C, and reaction methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 10mL uses second
Alcohol washes twice, and obtains elastomer polymer.Yield: 74%, number-average molecular weight (Mn): 52468, molecular weight distribution (PDI):
3.8.Different structure proportion: cis-1,4- structure account for 40%, trans-1, and 4- structure accounts for 11%, and 3,4- structures account for 49%.
Embodiment 12
Under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially add dry toluene 5mL, methylaluminoxane
(8mmol), isoprene (2mL, 20.0mmol), the 1mL dichloro for the catalyst (2.48mg, 8 μm of ol) that embodiment 1 is prepared
Dichloromethane, polymerize 2h at 25 DEG C, and reaction methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 10mL uses second
Alcohol washes twice, and obtains elastomer polymer.Yield: 75%, number-average molecular weight (Mn): 35178, molecular weight distribution (PDI):
3.6.Different structure proportion: cis-1,4- structure account for 45%, trans-1, and 4- structure accounts for 15%, and 3,4- structures account for 40%.
Embodiment 13
Under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially add dry toluene 5mL, methylaluminoxane
(2mmol), isoprene (2mL, 20.0mmol), the 1mL dichloro for the catalyst (2.48mg, 8 μm of ol) that embodiment 1 is prepared
Dichloromethane, polymerize 2h at 25 DEG C, and reaction methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 10mL uses second
Alcohol washes twice, and obtains elastomer polymer.Yield: 68%, number-average molecular weight (Mn): 56328, molecular weight distribution (PDI):
3.0.Different structure proportion: cis-1,4- structure account for 48%, trans-1, and 4- structure accounts for 11%, and 3,4- structures account for 41%.
Embodiment 14
Under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially add dry toluene 5mL, methylaluminoxane
(0.8mmol), isoprene (2mL, 20.0mmol), the 1mL bis- for the catalyst (2.48mg, 8 μm of ol) that embodiment 1 is prepared
Chloromethanes solution, polymerize 2h at 25 DEG C, and reaction methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 10mL is used
Ethanol washing twice, obtains elastomer polymer.Yield: 55%, number-average molecular weight (Mn): 34958, molecular weight distribution (PDI):
2.8.Different structure proportion: cis-1,4- structure account for 45%, trans-1, and 4- structure accounts for 10%, and 3,4- structures account for 45%.
Embodiment 15
Under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially add anhydrous hexane 5mL, methylaluminoxane
(0.16mmol), isoprene (2mL, 20.0mmol), the 1mL for the catalyst (2.48mg, 8 μm of ol) that embodiment 1 is prepared
Dichloromethane solution polymerize 2h at 25 DEG C, reacts methanolic HCl solution (MeOH/HCl=50/1) quenching reaction for using 10mL,
Twice with ethanol washing, elastomer polymer is obtained.Polymer is not obtained.
Embodiment 16
Under argon atmosphere, wished in Lake (Schlenk) pipe in 25mL, successively dry toluene 5mL, methylaluminoxane
The 1mL dichloromethane solution for the catalyst (2.48mg, 8 μm of ol) that (4mmol) and embodiment 1 are prepared, is then added isoamyl
Diene (2mL, 20.0mmol), polymerize 2h at 25 DEG C, and reaction is quenched with the methanolic HCl solution (MeOH/HCl=50/1) of 10mL
Reaction of going out twice with ethanol washing obtains elastomer polymer.Yield: 78%, number-average molecular weight (Mn): 46482, molecular weight
It is distributed (PDI): 3.0.Different structure proportion: cis-1,4- structure account for 46%, trans-1, and 4- structure accounts for 10%, 3,4- knots
Structure accounts for 44%.
Embodiment 17
Under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially add the catalysis that embodiment 1 is prepared
Agent (2.48mg, 8 μm of ol), methylaluminoxane is then added in dry toluene 5mL, isoprene (2mL, 20.0mmol)
(4mmol), polymerize 2h, the reaction methanolic HCl solution (MeOH/HCl=50/1) of 10mL at 25 DEG C, and quenching reaction uses second
Alcohol washes twice, and obtains elastomer polymer.Yield: 74%, number-average molecular weight (Mn): 53649, molecular weight distribution (PDI):
3.8.Different structure proportion: cis-1,4- structure account for 43%, trans-1, and 4- structure accounts for 7%, and 3,4- structures account for 50%.
Embodiment 18
Under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially add anhydrous tetrahydro furan 5mL, aluminium methyl
Oxygen alkane (4mmol), isoprene (2mL, 20.0mmol), the 1mL for the catalyst (2.48mg, 8 μm of ol) that embodiment 1 is prepared
Dichloromethane solution polymerize 2h at 25 DEG C, reacts methanolic HCl solution (MeOH/HCl=50/1) quenching reaction for using 10mL,
Polymer is not obtained.
Embodiment 19
Under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially add anhydrous hexane 5mL, methylaluminoxane
(4mmol), isoprene (2mL, 20.0mmol), the 1mL dichloro for the catalyst (2.48mg, 8 μm of ol) that embodiment 1 is prepared
Dichloromethane, polymerize 2h at 25 DEG C, and reaction methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 10mL uses second
Alcohol washes twice, and obtains elastomer polymer.Yield: 70%, number-average molecular weight (Mn): 32498, molecular weight distribution (PDI):
3.4.Different structure proportion: cis-1,4- structure account for 55%, trans-1, and 4- structure accounts for 8%, and 3, -4 structures account for 37%.
Embodiment 20
Under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially add anhydrous pentane 5mL, methylaluminoxane
(4mmol), isoprene (2mL, 20.0mmol), the 1mL dichloro for the catalyst (2.48mg, 8 μm of ol) that embodiment 1 is prepared
Dichloromethane, polymerize 2h at 25 DEG C, and reaction methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 10mL uses second
Alcohol washes twice, and obtains elastomer polymer.Yield: 69%, number-average molecular weight (Mn): 34667, molecular weight distribution (PDI):
4.8.Different structure proportion: cis-1,4- structure account for 42%, trans-1, and 4- structure accounts for 16%, and 3,4- structures account for 42%.
Embodiment 22
Under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially add dry toluene 5mL, methylaluminoxane
(4mmol), isoprene (2mL, 20.0mmol), the 1mL dichloro for the catalyst (2.48mg, 8 μm of ol) that embodiment 1 is prepared
Dichloromethane, polymerize 2h at 50 DEG C, and reaction methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 10mL uses second
Alcohol washes twice, and obtains elastomer polymer.Yield: 35%, number-average molecular weight (Mn): 24835, molecular weight distribution (PDI):
3.2.Different structure proportion: cis-1,4- structure account for 49%, trans-1, and 4- structure accounts for 11%, and 3,4- structures account for 40%.
Embodiment 22
Under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially add dry toluene 5mL, methylaluminoxane
(4mmol), isoprene (2mL, 20.0mmol), the 1mL dichloro for the catalyst (2.48mg, 8 μm of ol) that embodiment 1 is prepared
Dichloromethane, polymerize 2h at 0 DEG C, and reaction methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 10mL uses second
Alcohol washes twice, and obtains elastomer polymer.Yield: 60%, number-average molecular weight (Mn): 71269, molecular weight distribution (PDI):
4.0.Different structure proportion: cis-1,4- structure account for 49%, trans-1, and 4- structure accounts for 11%, and 3,4- structures account for 40%.
Embodiment 23
Under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially add dry toluene 5mL, methylaluminoxane
(4mmol), isoprene (2mL, 20.0mmol), the 1mL dichloro for the catalyst (2.48mg, 8 μm of ol) that embodiment 1 is prepared
Dichloromethane, polymerize 2h at -25 DEG C, and reaction methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 10mL is used
Ethanol washing twice, obtains elastomer polymer.Yield: 30%, number-average molecular weight (Mn): 75589, molecular weight distribution (PDI):
2.5.Different structure proportion: cis-1,4- structure account for 48%, trans-1, and 4- structure accounts for 10%, and 3,4- structures account for 42%.
Embodiment 24
Under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially add dry toluene 5mL, methylaluminoxane
(4mmol), isoprene (2mL, 20.0mmol), the 1mL dichloro for the catalyst (3.28mg, 8 μm of ol) that embodiment 2 is prepared
Dichloromethane, polymerize 2h at 25 DEG C, and reaction methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 10mL uses second
Alcohol washes twice, and obtains elastomer polymer.Yield: 52%, number-average molecular weight (Mn): 46422, molecular weight distribution (PDI):
3.1.Different structure proportion: cis-1,4- structure account for 74%, trans-1, and 4- structure accounts for 0%, and 3,4 structures account for 26%.
Embodiment 25
Under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially add dry toluene 5mL, methylaluminoxane
(4mmol), isoprene (2mL, 20.0mmol), the 1mL dichloro for the catalyst (5.26mg, 8 μm of ol) that embodiment 3 is prepared
Dichloromethane, polymerize 2h at 25 DEG C, and reaction methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 10mL uses second
Alcohol washes twice, and obtains elastomer polymer.Yield: 72%, number-average molecular weight (Mn): 38249, molecular weight distribution (PDI):
2.8.Different structure proportion: cis-1-, 4- structure account for 80%, trans-1, and 4- structure accounts for 0%, and 3,4- structures account for 20%.
Embodiment 26
Under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially add dry toluene 5mL, methylaluminoxane
(4mmol), isoprene (2mL, 20.0mmol), the 1mL dichloro for the catalyst (3.02mg, 8 μm of ol) that embodiment 4 is prepared
Dichloromethane, polymerize 2h at 25 DEG C, and reaction methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 10mL uses second
Alcohol washes twice, and obtains elastomer polymer.Yield: 63%, number-average molecular weight (Mn): 42105, molecular weight distribution (PDI):
3.4.Different structure proportion: cis-1-, 4- structure account for 50%, trans-1, and 4- structure accounts for 11%, and 3,4- structures account for 39%.
Embodiment 27
Under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially add dry toluene 5mL, methylaluminoxane
(4mmol), isoprene (2mL, 20.0mmol), the 1mL dichloro for the catalyst (2.91mg, 8 μm of ol) that embodiment 5 is prepared
Dichloromethane, polymerize 2h at 25 DEG C, and reaction methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 10mL uses second
Alcohol washes twice, and obtains elastomer polymer.Yield: 23%, number-average molecular weight (Mn): 39892, molecular weight distribution (PDI):
2.4.Different structure proportion: cis-1-, 4- structure account for 45%, trans-1, and 4- structure accounts for 10%, and 3,4- structures account for 45%.
Embodiment 28
Under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially add dry toluene 5mL, methylaluminoxane
(4mmol), isoprene (2mL, 20.0mmol), the 1mL dichloro for the catalyst (2.72mg, 8 μm of ol) that embodiment 6 is prepared
Dichloromethane, polymerize 2h at 25 DEG C, and reaction methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 10mL uses second
Alcohol washes twice, and obtains elastomer polymer.Yield: 56%, number-average molecular weight (Mn): 34289, molecular weight distribution (PDI):
2.6.Different structure proportion: cis-1-, 4- structure account for 55%, trans-1, and 4- structure accounts for 10%, and 3,4- structures account for 35%.
Embodiment 29
Under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially add dry toluene 5mL, trimethyl aluminium
(0.16mmol), the 2mL dichloromethane solution of catalyst (2.48mg, 8 μm of ol) prepared by embodiment 1 stir 2min, and boron is added
Salt [CPh3][B(C6F5)4] (8 μm of ol), 2min is stirred, isoprene (2mL, 20mmol) polymerize 2h at 25 DEG C, and reaction is used
Methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 10mL twice with ethanol washing obtains elastomer polymer.It produces
Rate: 65%, number-average molecular weight (Mn): 12245, molecular weight distribution (PDI): 2.8.Different structure proportion: cis-1,4- knot
Structure accounts for 42%, trans-1, and 4- structure accounts for 14%, and 3,4- structures account for 34%.
Embodiment 30
Under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially add dry toluene 5mL, triethyl aluminum
(0.16mmol), the 2mL dichloromethane solution of catalyst (2.48mg, 8 μm of ol) prepared by embodiment 1 stir 2min, and boron is added
Salt [CPh3][B(C6F5)4] (8 μm of ol), 2min is stirred, isoprene (2mL, 20mmol) polymerize 2h at 25 DEG C, and reaction is used
Methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 10mL twice with ethanol washing obtains elastomer polymer.It produces
Rate: 58%, number-average molecular weight (Mn): 10389, molecular weight distribution (PDI): 3.2.Different structure proportion: cis-1,4- knot
Structure accounts for 48%, trans-1, and 4- structure accounts for 13%, and 3,4- structures account for 39%.
Embodiment 31
Under argon atmosphere, is wished in Lake (Schlenk) pipe in 25mL, sequentially add dry toluene 5mL, triisobutyl aluminium
(0.16mmol), the 2mL dichloromethane solution of catalyst (2.48mg, 8 μm of ol) prepared by embodiment 1 stir 2min, and boron is added
Salt [CPh3][B(C6F5)4] (8 μm of ol), 2min is stirred, isoprene (2mL, 20mmol) polymerize 2h at 25 DEG C, and reaction is used
Methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 10mL twice with ethanol washing obtains elastomer polymer.It produces
Rate: 60%, number-average molecular weight (Mn): 15486, molecular weight distribution (PDI): 2.6.Different structure proportion: cis-1,4- knot
Structure accounts for 46%, trans-1, and 4- structure accounts for 6%, and 3,4- structures account for 48%.
The data setting such as following table of section Example.
Above-described embodiment is preferable case study on implementation of the invention, but case study on implementation of the invention is not by enumerating embodiment
Limitation, other any changes made without departing from core of the invention thought with principle, modification, combine, substitution, simplify be accordingly to be regarded as
Equivalent substitution should be all included within protection scope of the present invention.
Claims (9)
1. a kind of aryl substituted pyridine amine Fe-series catalyst, it is characterised in that: be made of major catalyst and co-catalyst, main catalytic
Agent is pyridine amine iron complex, and general structural Formula isWherein, R1For phenyl, substituted-phenyl or substitution virtue
Heterocycle；R2For H, methyl, ethyl or phenyl；R3For hydrogen, alkyl, aryl or halogen；Co-catalyst be methylaluminoxane (MAO) or
Alkyl aluminum AlR3, the methylaluminoxane general structure isWherein n is the natural number of 4-40, and the alkyl aluminum is
Trimethyl aluminium, triethyl aluminum, one of triisobutyl aluminium；The ferro element in aluminium element and major catalyst in co-catalyst
Molar ratio is (100-2000): 1.
2. Fe-series catalyst according to claim 1, it is characterised in that: the pyridine amine iron complex structural formula is following
One of structural formula:
3. a kind of preparation method of pyridine amine iron complex of any of claims 1 or 2, it is characterised in that: in anhydrous DCM,
By pyridine amine ligand and anhydrous FeCl2With molar ratio 1:1 mixing, it is stirred to react 24-48h at room temperature, it is after post treatment, final dry
It is dry to obtain pyridine amine iron complex.
4. method according to claim 3, it is characterised in that: the pyridine amine ligand structural formula is one in following structural formula
Kind:
5. a kind of application of catalyst of any of claims 1 or 2 in isoprene polymerization, it is characterised in that: in anhydrous nothing
Under the conditions of oxygen, pyridine amine iron complex, isoprene monomer, co-catalyst and solvent is added into reactor and forms reactant
System, then polymerization reaction occurs for stirring, quencher is added after reaction, twice with ethanol washing, separating-purifying obtains gathering different
Pentadiene product.
6. application according to claim 5, it is characterised in that: the solvent be one of toluene, pentane or hexane or
Two kinds or more so that the concentration of isoprene monomer is 4mol/L.
7. application according to claim 5, it is characterised in that: in reaction system, monomer isoprene and Fe-series catalyst
The molar ratio of ferro element is (1000-5000) in middle major catalyst: 1.
8. application according to claim 5, it is characterised in that: the temperature of the polymerization reaction is 0 DEG C -50 DEG C, when polymerization
Between be 1-4h.
9. application according to claim 5, it is characterised in that: it further include dealkylating reagent in the reaction system, institute
Stating dealkylating reagent is B (C6F5)3, [Ph3C][B(C6F5)4],[PhNMe2H][B(C6F5)4] one kind；Dealkylating reagent
Ferro element molar ratio is (1-10) in middle boron element and major catalyst: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810864108.3A CN109134730B (en) | 2018-08-01 | 2018-08-01 | Aryl substituted pyridylamine iron catalyst, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810864108.3A CN109134730B (en) | 2018-08-01 | 2018-08-01 | Aryl substituted pyridylamine iron catalyst, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109134730A true CN109134730A (en) | 2019-01-04 |
| CN109134730B CN109134730B (en) | 2021-03-12 |
Family
ID=64798638
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810864108.3A Active CN109134730B (en) | 2018-08-01 | 2018-08-01 | Aryl substituted pyridylamine iron catalyst, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109134730B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109851700A (en) * | 2019-03-11 | 2019-06-07 | 中国科学院青岛生物能源与过程研究所 | A kind of trident pyridinimine Fe-series catalyst and the preparation method and application thereof |
| CN109912732A (en) * | 2019-03-11 | 2019-06-21 | 中国科学院青岛生物能源与过程研究所 | A kind of bonding pyridine amine Fe-series catalyst and the preparation method and application thereof |
| CN111303214A (en) * | 2020-03-27 | 2020-06-19 | 中国科学院青岛生物能源与过程研究所 | Pyridine tertiary amine iron complex, preparation method thereof and method for catalyzing polymerization of conjugated diene by using same |
| CN112175123A (en) * | 2020-09-27 | 2021-01-05 | 中国科学院青岛生物能源与过程研究所 | Poly-conjugated diene liquid rubber and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2018073795A1 (en) * | 2016-10-20 | 2018-04-26 | Versalis S.P.A. | Process for preparing conjugated diene (co)polymers in the presence of a catalytic system comprising a pyridyl iron (iii) complex |
| CA3036579A1 (en) * | 2016-10-20 | 2018-04-26 | Versalis S.P.A. | Process for the preparation of syndiotactic 1,2-polybutadiene in the presence of a catalytic system comprising a pyridyl iron complex |
-
2018
- 2018-08-01 CN CN201810864108.3A patent/CN109134730B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2018073795A1 (en) * | 2016-10-20 | 2018-04-26 | Versalis S.P.A. | Process for preparing conjugated diene (co)polymers in the presence of a catalytic system comprising a pyridyl iron (iii) complex |
| CA3036579A1 (en) * | 2016-10-20 | 2018-04-26 | Versalis S.P.A. | Process for the preparation of syndiotactic 1,2-polybutadiene in the presence of a catalytic system comprising a pyridyl iron complex |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109851700A (en) * | 2019-03-11 | 2019-06-07 | 中国科学院青岛生物能源与过程研究所 | A kind of trident pyridinimine Fe-series catalyst and the preparation method and application thereof |
| CN109912732A (en) * | 2019-03-11 | 2019-06-21 | 中国科学院青岛生物能源与过程研究所 | A kind of bonding pyridine amine Fe-series catalyst and the preparation method and application thereof |
| CN109912732B (en) * | 2019-03-11 | 2021-04-27 | 中国科学院青岛生物能源与过程研究所 | Bond-forming pyridylamine iron-based catalyst and preparation method and application thereof |
| CN111303214A (en) * | 2020-03-27 | 2020-06-19 | 中国科学院青岛生物能源与过程研究所 | Pyridine tertiary amine iron complex, preparation method thereof and method for catalyzing polymerization of conjugated diene by using same |
| CN111303214B (en) * | 2020-03-27 | 2023-02-17 | 中国科学院青岛生物能源与过程研究所 | Pyridine tertiary amine iron complex, preparation method thereof and method for catalyzing polymerization of conjugated diene by using same |
| CN112175123A (en) * | 2020-09-27 | 2021-01-05 | 中国科学院青岛生物能源与过程研究所 | Poly-conjugated diene liquid rubber and preparation method and application thereof |
| CN112175123B (en) * | 2020-09-27 | 2022-09-27 | 中国科学院青岛生物能源与过程研究所 | Poly-conjugated diene liquid rubber and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109134730B (en) | 2021-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109134730A (en) | A kind of aryl substituted pyridine amine Fe-series catalyst and the preparation method and application thereof | |
| CN108530571B (en) | Iron-based alkylpyridinylimine catalyst and preparation method and application thereof | |
| CN109851700A (en) | A kind of trident pyridinimine Fe-series catalyst and the preparation method and application thereof | |
| CN106632764B (en) | A kind of Fe-series catalyst and preparation method thereof and the application in isoprene polymerization | |
| CN109053937A (en) | A kind of alkyl substituted pyridines amine Fe-series catalyst and the preparation method and application thereof | |
| CN109912732A (en) | A kind of bonding pyridine amine Fe-series catalyst and the preparation method and application thereof | |
| CN108586641B (en) | High-efficiency iron-based catalyst for catalyzing isoprene polymerization and preparation method and application thereof | |
| Cui | Molecular catalysis of rare-earth elements | |
| CN110305169B (en) | Substituted bipyridyl ferric iron complex and preparation method and application thereof | |
| Appukuttan et al. | Stereospecific polymerizations of 1, 3-butadiene catalyzed by Co (II) complexes ligated by 2, 6-bis (benzimidazolyl) pyridines | |
| CN111303214B (en) | Pyridine tertiary amine iron complex, preparation method thereof and method for catalyzing polymerization of conjugated diene by using same | |
| CN110283264A (en) | A kind of bipyridyl iron complex and the preparation method and application thereof | |
| CN105037588B (en) | A kind of iso-indoles rare-earth metal catalyst, preparation method and application | |
| CN108641026B (en) | Application of benzyl imine pyridine iron complex in preparation of isoprene rubber | |
| CN102659961B (en) | Cobalt catalyst and application thereof in 1,3-butadiene polymerization reaction | |
| CN108659055B (en) | Iron complex based on flexible framework, preparation method thereof and application thereof in isoprene polymerization | |
| CN108484809B (en) | Olefin polymerization catalyst | |
| CN107312115B (en) | Bis-indole rare earth metal catalyst, preparation method and application | |
| CN104151454B (en) | A kind of cobalt series catalyst and the application in 1,3-butadiene polymerization thereof | |
| CN110305168A (en) | A kind of substitution bipyridyl ferrous coordination compound and the preparation method and application thereof | |
| CN112409539A (en) | Butadiene-isoprene copolymer and preparation method thereof | |
| CN112707937B (en) | Heteroaromatic ring tridentate pyridine imine iron complex, preparation method thereof and application thereof in catalysis of polymerization of conjugated diene | |
| CN112142893B (en) | Polyisoprene and preparation method thereof | |
| CN108341903B (en) | Olefin polymerization catalyst | |
| CN108641022A (en) | Rare earth catalyst and preparation method thereof and syndiotactic polymerization process of phenylethylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |