CN110396150A - A kind of poly- conjugated alkene of iron series super high molecular weight and preparation method thereof - Google Patents
A kind of poly- conjugated alkene of iron series super high molecular weight and preparation method thereof Download PDFInfo
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- 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
- C08F136/06—Butadiene
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- 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
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- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/70—Iron group metals, platinum group metals or compounds thereof
- C08F4/7001—Iron group metals, platinum group metals or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
- C08F4/7003—Bidentate ligand
- C08F4/7004—Neutral ligand
- C08F4/7006—NN
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Abstract
The invention discloses a kind of poly- conjugated alkene of iron series super high molecular weight and preparation method thereof, it is related to a kind of super high molecular weight, poly- conjugated alkene rubber structure of high branched structure and preparation method thereof.The present invention adopts the specific iron catalyst system of molecular structure and prepares super high molecular weight polymer；Catalyst system is simple, high catalytic efficiency, and the production cost of polymer is low.The poly- conjugated alkene rubber, it is characterised in that the molecular weight of polymerization belongs to super high molecular weight, and has a large amount of side group on the chain element of rubber, is mainly used for it and prepares that wet-sliding resistant performance is good and the high-performance tire and other relevant rubber products of low friction heat.
Description
Technical field
The invention belongs to poly- conjugated alkene field of rubber materials, and in particular to a kind of super high molecular weight and contain high side chain radical
Poly- conjugated alkene rubber structure and preparation method thereof.
Background technique
For a long time, the rolling resistance of tyre stock and anti-slippery this hamper " green tire " development always to contradiction
It promotes, anti-form-1,4- polyisoprene rubber (TPI), high vinyl polybutadiene rubber (HVBR) and 3,4- polyisoprene
The appearance of the new materials such as rubber (3,4-PIP) opened up a new way for the research application of " green tire ".High-vinyl polybutadiene
Alkene rubber (HVBR) and 3,4- polyisoprene (3,4-PIP) have high wet-sliding resistant performance, low rolling resistance and good
Damping performance can be used for manufacturing high-performance tire；The water resistance and air-tightness of this rubber are close to butyl rubber；It also can be with second third
Rubber blending prepares the vulcanizate of high service performance, meets the technique requirement of manufacture vehicle section bar.Currently, this general is birdsed of the same feather flock together altogether
The molecular weight of yoke alkene is again between ten thousand g/mol of 20-60, and the molecular weight for improving polymerization can significantly improve the physics of polymer
Performance and mechanical property, can significantly increase erosion-resisting characteristics, the resistance to low temperature of polymer, and Wear-resistant corrosion-resistant is to can replace portion
The ideal type polymer of steel splitting iron application every field.It can also be blended simultaneously with other high polymers multiple to prepare novel multicomponent
Condensation material.
Summary of the invention
The strand that there is super high molecular weight polymer high molecular weight, height to tangle assigns its excellent mechanical property
Energy.For solve the problems, such as defect existing in the prior art and, provide more good preparation method and product, the present invention proposes one kind
Super high molecular weight, poly- conjugated alkene of Gao Zhilian and preparation method thereof.
The content of present invention is as follows:
A kind of poly- conjugated alkene of iron series super high molecular weight: poly- conjugated alkene rubber 3,4- (1,2-) structural content is
60-80%, Isosorbide-5-Nitrae structural content are 20-40%, and the range of number-average molecular weight of poly- conjugated alkene is ten thousand g/mol of 100-300, molecule
Amount distribution 1.5-5.0.
The poly- conjugated alkene is polyisoprene, polybutadiene and polyisoprene-butadiene copolymer.
The poly- conjugated alkene rubber, it is characterised in that the molecular weight of polymerization belongs to super high molecular weight, the branch of polymer
Chain degree belongs to high branch degree, due to having a large amount of side group on the chain element of its rubber, is mainly used for it and prepares wet-sliding resistant performance
Good and low friction heat high-performance tire and other relevant rubber products.
The poly- conjugated alkene of iron series super high molecular weight, catalyst system used in preparation process are as follows: bipyridyl
Iron complex is major catalyst, alkyl aluminum is co-catalyst and (or) boron salt is alkylation removal reagent, wherein the bipyridyl iron
Complex structure formula is one of following structural formula:
The present invention also provides the preparation methods of above-mentioned poly- conjugated alkene, including method one or method two:
Method one: under inert gas atmosphere, solvent and conjugate diene monomer are sequentially added into reactor and is stirred, then
The premix system including bipyridyl iron complex, co-catalyst and (or) alkylation removal reagent is added, in -20-50 DEG C (preferably 25
DEG C) constant temperature polymerization 10min-720min (preferably 120min), quencher and age resister are added after reaction, uses ethanol washing
Twice, separating-purifying obtains polymerized conjugated diene；
Method two: under inert gas atmosphere, bipyridyl iron complex, solvent, co-catalyst are sequentially added into reactor
And (or) alkylation removal reagent and stir, conjugate diene monomer is then added, polymerize in -20-50 DEG C of (preferably 25 DEG C) constant temperature
Quencher and age resister is added in 10min-720min (preferably 120min) after reaction, and twice with ethanol washing, separation mentions
It is pure to obtain polymerized conjugated diene.
The co-catalyst is selected from triethyl aluminum, triisobutyl aluminium, trimethyl aluminium, methylaluminoxane and modified methyl aluminium
One or both of oxygen alkane, preferably methylaluminoxane.
The alkylation removal reagent is [Ph3C][B(C6F5)4], [PhNMe2H][B(C6H5)4] and [Ph3C][BF4] in
One kind, preferably [Ph3C][B(C6F5)4]。
Wherein the molar ratio of the ferro element in bipyridyl iron complex and olefinic monomer is 1:(2500-25000), preferably 1:
10000, the molar ratio of ferro element is (10-1000) in aluminium element and bipyridyl iron complex in co-catalyst: 1, preferably 200:
1, the molar ratio of ferro element is (1-20): 1, preferably 1:1, solvent and alkene list in alkylation removal reagent and bipyridyl iron complex
The volume ratio of body is (5-50): 1, preferably 10:1.
The solvent selects hexane, normal heptane, hexamethylene, pentane, petroleum ether and toluene one or two kinds of, preferably hexane.
The catalyst system including bipyridyl iron complex, co-catalyst and alkylation removal reagent, is made before use
Pre-mixing agent, pre-mixing agent in Schlenk bottles of 25mL, sequentially add toluene, bipyridyl iron the preparation method comprises the following steps: under argon atmosphere
Complex (1equiv.), co-catalyst (200equiv), and stir 1min；Or sequentially add toluene, bipyridyl iron complex
(1equiv.), co-catalyst (20equiv) and alkylation removal reagent (1equiv.)
Beneficial effect
The present invention is using cheap iron as metal center, using bipyridyl as main skeleton, provides a kind of new and effective iron catalysis
Agent system.Two are conjugated as major catalyst, methylaluminoxane (MAO) as co-catalyst catalysis using bipyridyl ferrous metal complex
The polymerization of alkene, polymer provided by the invention have ultra-high molecular weight (number-average molecular weight is 1,000,000-300 ten thousand g/mol), height
The polymer of branch (3,4- (1,2-) structural content is 60-80%) narrower molecular weight distribution (PDI=1.5-5.0).It is acquired
Technical effect be summarized as follows:
1, poly- conjugated alkene number-average molecular weight of the present invention is 1,000,000-300 ten thousand, molecular weight distribution 1.5-5.0；
3,4- (1,2-) structural content proportion ranges are 60%-80%, and Isosorbide-5-Nitrae structure proportion range is 20%-40%.
2, iron catalyst system of the present invention is the specific bipyridyl iron complex of molecular structure, has preparation simple easy
, activity is high, and the more similar frerrous chloride complex compound of dissolubility of the acetylacetone,2,4-pentanedione iron complex in alkane greatly increases, so that instead
The efficiency and branch answered selectively also increased, and the cost of polymerization is low, the prospect with industrial applications.
3, polymerization reaction of the present invention can both carry out in two components of methylaluminoxane, can also be in alkyl aluminum
It is carried out in three components of alkylation removal reagent composition.
Detailed description of the invention
The GPC figure of super high molecular weight polyisoprene prepared by Fig. 1 embodiment 1；
Super high molecular weight polyisoprene prepared by Fig. 2 embodiment 11HNMR figure；
The DSC figure of super high molecular weight polyisoprene prepared by Fig. 3 embodiment 1；
Fig. 4 embodiment 7 prepares the GPC figure of super high molecular weight polybutadiene；
Super high molecular weight polybutadiene prepared by Fig. 5 embodiment 71HNMR figure；
The DSC figure of super high molecular weight polybutadiene prepared by Fig. 6 embodiment 7；
Fig. 7 embodiment 8 prepares super high molecular weight polyisoprene-butadiene GPC figure；
Super high molecular weight polyisoprene-butadiene prepared by Fig. 8 embodiment 81HNMR figure；
Super high molecular weight polyisoprene-butadiene DSC figure prepared by Fig. 9 embodiment 8.
Specific embodiment
The present invention will be further described combined with specific embodiments below, but the present invention should not be limited by the examples.
Embodiment 1
Under argon atmosphere, in Schlenk bottles of 250mL, anhydrous hexane 100mL is sequentially added, isoprene 10mL is simultaneously
1min is stirred, the premixed liquid prepared is then added and (under argon atmosphere, in Schlenk bottles of 25mL, sequentially adds catalysis
Agent 1 (4.1mg, 10 μm of ol), toluene 5mL and MAO (2mmol, 200eq.) simultaneously stir 1min.) it polymerize 120min at 25 DEG C, instead
Using methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 50mL, and age resister 2mL is added.With ethanol washing two
It is secondary, obtain solid white polymer.Yield: > 99%, number-average molecular weight (Mn): 1,120,000, molecular weight distribution (PDI): 1.9.No
With structure proportion: cis-1,4- structure account for 28%, and 3,4- structures account for 72%.
Embodiment 2 (changes charging sequence)
Under argon atmosphere, in Schlenk bottles of 250mL, sequentially add catalyst 1 (4.1mg, 10 μm of ol), it is anhydrous oneself
Alkane 100mL, MAO (2mmol, 200eq.) stir 1min, and isoprene (10mL, 100mmol) then is added.It polymerize at 25 DEG C
Methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 50mL is used in 120min, reaction, and age resister 2mL is added.With
Ethanol washing twice, obtains solid white polymer.Yield: > 99%, number-average molecular weight (Mn): 1,250,000, molecular weight distribution
(PDI): 1.5.Different structure proportion: cis-1,4- structure account for 23%, and 3,4- structures account for 77%.
Embodiment 3 (three components)
Under argon atmosphere, in Schlenk bottles of 250mL, anhydrous hexane 100mL is sequentially added, isoprene 10mL is simultaneously
1min is stirred, the premixed liquid prepared is then added and (under argon atmosphere, in Schlenk bottles of 25mL, sequentially adds toluene
5mL, catalyst 1 (4.1mg, 10 μm of ol) and Al (i-Bu)3(500 μm of ol, 50eq.) simultaneously stirs 1min, and [Ph is then added3C][B
(C6F5)4] (10 μm of ol, 1eq.) and stir 1min.) it polymerize 120min, the reaction methanolic HCl solution of 50mL at 25 DEG C
(MeOH/HCl=50/1) quenching reaction, and age resister 2mL is added.Twice with ethanol washing, solid white polymer is obtained.
Yield: > 99%, number-average molecular weight (Mn): 2,080,000, molecular weight distribution (PDI): 2.5.Different structure proportion: cis-1,4-
Structure accounts for 26%, and 3,4- structures account for 74%.
Embodiment 4 (different catalyst)
Under argon atmosphere, in Schlenk bottles of 250mL, anhydrous hexane 100mL is sequentially added, isoprene 10mL is simultaneously
1min is stirred, the premixed liquid prepared is then added and (under argon atmosphere, in Schlenk bottles of 25mL, sequentially adds catalysis
Agent 2 (4.4mg, 10 μm of ol), toluene 5mL and MAO (2mmol, 200eq.) simultaneously stir 1min.) it polymerize 120min at 25 DEG C, instead
Using methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 50mL, and age resister 2mL is added.With ethanol washing two
It is secondary, obtain solid white polymer.Yield: > 99%, number-average molecular weight (Mn): 1,300,000, molecular weight distribution (PDI): 1.9.No
With structure proportion: cis-1,4- structure account for 23%, and 3,4- structures account for 77%.
Embodiment 5
Under argon atmosphere, in Schlenk bottles of 250mL, anhydrous hexane 100mL is sequentially added, isoprene 10mL is simultaneously
1min is stirred, the premixed liquid prepared is then added and (under argon atmosphere, in Schlenk bottles of 25mL, sequentially adds catalysis
Agent 3 (5.1mg, 10 μm of ol), toluene 5mL and MAO (2mmol, 200eq.) simultaneously stir 1min.) it polymerize 120min at 25 DEG C, instead
Using methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 50mL, and age resister 2mL is added.With ethanol washing two
It is secondary, obtain solid white polymer.Yield: > 99%, number-average molecular weight (Mn): 1,140,000, molecular weight distribution (PDI): 1.6.No
With structure proportion: cis-1,4- structure account for 28%, and 3,4- structures account for 72%.
Embodiment 6
Under argon atmosphere, in Schlenk bottles of 250mL, anhydrous hexane 100mL is sequentially added, isoprene 10mL is simultaneously
1min is stirred, the premixed liquid prepared is then added and (under argon atmosphere, in Schlenk bottles of 25mL, sequentially adds catalysis
Agent 4 (5.4mg, 10 μm of ol), toluene 5mL and MAO (2mmol, 200eq.) simultaneously stir 1min.) it polymerize 120min at 25 DEG C, instead
Using methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 50mL, and age resister 2mL is added.With ethanol washing two
It is secondary, obtain solid white polymer.Yield: > 99%, number-average molecular weight (Mn): 1,380,000, molecular weight distribution (PDI): 2.1.No
With structure proportion: cis-1,4- structure account for 25%, and 3,4- structures account for 75%.
Embodiment 7 (butadiene)
Under argon atmosphere, in Schlenk bottles of 250mL, anhydrous hexane 100mL is sequentially added, butadiene 10mL is simultaneously stirred
1min is mixed, the premixed liquid prepared is then added and (under argon atmosphere, in Schlenk bottles of 25mL, sequentially adds catalyst 1
(4.1mg, 10 μm of ol), toluene 5mL and MAO (2mmol, 200eq.) simultaneously stir 1min.) it polymerize 120min at 25 DEG C, it reacts
With methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 50mL, and age resister 2mL is added.With ethanol washing two
It is secondary, obtain solid white polymer.Yield: > 99%, number-average molecular weight (Mn): 1,200,000, molecular weight distribution (PDI): 1.7.No
With structure proportion: cis-1,4- structure account for 25%, and 1,2- structure accounts for 75%.
Embodiment 8 (isoprene and butadiene copolymer)
Under argon atmosphere, in Schlenk bottles of 250mL, sequentially add anhydrous hexane 100mL, isoprene 5mL and
Butadiene 5mL simultaneously stirs 1min, be then added prepare premixed liquid (under argon atmosphere, in Schlenk bottles of 25mL, according to
Secondary addition catalyst 1 (4.1mg, 10 μm of ol), toluene 5mL and MAO (2mmol, 200eq.) simultaneously stir 1min.) gather at 25 DEG C
120min is closed, methanolic HCl solution (MeOH/HCl=50/1) quenching reaction of 50mL is used in reaction, and age resister 2mL is added.
Twice with ethanol washing, solid white polymer is obtained.Yield: > 99%, number-average molecular weight (Mn): 1,810,000, molecular weight distribution
(PDI): 1.4.Different structure proportion: isoprene section: butadiene section=1:1, isoprene section: cis-1,4- structure account for
28%, 3,4- structures account for 72%.Butadiene section: cis-1,4- structure account for 33%, and 1,2- structure accounts for 67%.
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 (10)
1. a kind of poly- conjugated alkene of iron series super high molecular weight, it is characterised in that: 3,4- (1,2-) in the poly- conjugated alkene rubber
Structural content is 60-80%, and Isosorbide-5-Nitrae structural content is 20-40%, and the range of number-average molecular weight of poly- conjugated alkene is 100-300 ten thousand
G/mol, molecular weight distribution 1.5-5.0.
2. the poly- conjugated alkene of iron series super high molecular weight as described in claim 1, it is characterised in that: the poly- conjugated alkene is poly-
Isoprene, polybutadiene and polyisoprene-butadiene copolymer.
3. the poly- conjugated alkene of iron series super high molecular weight as described in claim 1, it is characterised in that: be used to prepare anti-slippery, low
The high-performance tire of frictional heat generation and other rubber products.
4. the poly- conjugated alkene of iron series super high molecular weight as described in claim 1, it is characterised in that: used in its preparation process
Catalyst system is as follows: bipyridyl iron complex is major catalyst, alkyl aluminum is co-catalyst and (or) boron salt is alkylation removal examination
Agent, wherein the bipyridyl iron complex structural formula is one of following structural formula:
5. a kind of preparation method of any one of claim 1-4 poly- conjugated alkene, it is characterised in that: including method one or side
Method two:
Method one: under inert gas atmosphere, solvent and conjugate diene monomer are sequentially added into reactor and is stirred evenly, then
The premix system including bipyridyl iron complex, co-catalyst and (or) alkylation removal reagent is added, it is poly- in -20-50 DEG C of constant temperature
10min-720min is closed, quencher and age resister are added after reaction, twice with ethanol washing, separating-purifying obtains poly- total
Yoke diene；
Method two: under inert gas atmosphere, sequentially added into reactor bipyridyl iron complex, solvent, co-catalyst and
(or) alkylation removal reagent and stir evenly, conjugate diene monomer is then added, polymerize 10min- in -20-50 DEG C of constant temperature
Quencher and age resister is added in 720min after reaction, and twice with ethanol washing, separating-purifying obtains polymerized conjugated diene.
6. the preparation method of poly- conjugated alkene as claimed in claim 5, it is characterised in that: the co-catalyst is triethyl group
One or both of aluminium, triisobutyl aluminium, trimethyl aluminium, methylaluminoxane and modified methylaluminoxane.
7. the preparation method of poly- conjugated alkene as claimed in claim 5, it is characterised in that: the alkylation removal reagent is
[Ph3C][B(C6F5)4], [PhNMe2H][B(C6H5)4] and [Ph3C][BF4One of].
8. the preparation method of poly- conjugated alkene as claimed in claim 6, it is characterised in that: wherein in bipyridyl iron complex
The molar ratio of ferro element and olefinic monomer is 1:(2500-25000), aluminium element and iron in bipyridyl iron complex in co-catalyst
The molar ratio of element is (10-1000): 1, the molar ratio of ferro element is (1- in alkylation removal reagent and bipyridyl iron complex
20): 1, the volume ratio of solvent and olefinic monomer is (5-50): 1.
9. the preparation method of poly- conjugated alkene as claimed in claim 5, it is characterised in that: the solvent is hexane, positive heptan
Alkane, hexamethylene, pentane, petroleum ether and toluene are one or two kinds of.
10. the preparation method of poly- conjugated alkene as claimed in claim 5, it is characterised in that: described includes that bipyridyl iron cooperates
Pre-mixing agent is made in the catalyst system of object, co-catalyst and alkylation removal reagent before use, and pre-mixing agent is the preparation method comprises the following steps: in argon
Under atmosphere is enclosed, in Schlenk bottles of 25mL, sequentially adds and toluene, bipyridyl iron complex (1equiv.), co-catalyst is added
(10-1000equiv), and stir 1min；Or sequentially add toluene, bipyridyl iron complex (1equiv.), co-catalyst
(10-1000equiv) and alkylation removal reagent (1equiv.), and stir 1min.
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Cited By (7)
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| CN112266432A (en) * | 2020-10-27 | 2021-01-26 | 中国科学院青岛生物能源与过程研究所 | Efficient preparation method of high molecular weight polylaurene with high 3, 4-structure content |
| WO2021042258A1 (en) * | 2019-09-03 | 2021-03-11 | 中国科学院青岛生物能源与过程研究所 | Bipyridine iron complex, preparation method thereof and application in polymerization of conjugated diene |
| CN112521538A (en) * | 2020-11-24 | 2021-03-19 | 中国科学院青岛生物能源与过程研究所 | Efficient preparation method and application of ultra-high molecular weight beta-farnesene |
| CN114805685A (en) * | 2022-04-21 | 2022-07-29 | 中国科学院青岛生物能源与过程研究所 | Polar conjugated olefin polymer and preparation method and application thereof |
| CN114874362A (en) * | 2022-03-18 | 2022-08-09 | 中国科学院青岛生物能源与过程研究所 | Pyridylenoxime iron catalyst, preparation method thereof and application thereof in conjugated diene polymerization |
| CN115073666A (en) * | 2022-07-05 | 2022-09-20 | 中国科学院青岛生物能源与过程研究所 | High molecular weight iron-based bio-based rubber, preparation method and application thereof, and rubber composition based on high molecular weight iron-based bio-based rubber |
| WO2024114510A1 (en) * | 2022-12-01 | 2024-06-06 | 中国科学院青岛生物能源与过程研究所 | Catalytic system for conjugated diene, and preparation method therefor and use thereof |
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| WO2018220538A1 (en) * | 2017-05-31 | 2018-12-06 | Versalis S.P.A. | Butadiene-isoprene diblock copolymers and process for the preparation thereof |
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| CN112521538A (en) * | 2020-11-24 | 2021-03-19 | 中国科学院青岛生物能源与过程研究所 | Efficient preparation method and application of ultra-high molecular weight beta-farnesene |
| CN114874362A (en) * | 2022-03-18 | 2022-08-09 | 中国科学院青岛生物能源与过程研究所 | Pyridylenoxime iron catalyst, preparation method thereof and application thereof in conjugated diene polymerization |
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| CN115073666A (en) * | 2022-07-05 | 2022-09-20 | 中国科学院青岛生物能源与过程研究所 | High molecular weight iron-based bio-based rubber, preparation method and application thereof, and rubber composition based on high molecular weight iron-based bio-based rubber |
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