CN107522660A - Imidazoleimines class part, its nickel complex and its application in polyisoprene synthesis - Google Patents
Imidazoleimines class part, its nickel complex and its application in polyisoprene synthesis Download PDFInfo
- Publication number
- CN107522660A CN107522660A CN201710877522.3A CN201710877522A CN107522660A CN 107522660 A CN107522660 A CN 107522660A CN 201710877522 A CN201710877522 A CN 201710877522A CN 107522660 A CN107522660 A CN 107522660A
- Authority
- CN
- China
- Prior art keywords
- imidazoleimines
- nickel complex
- catalyst
- polyisoprene
- solvent
- 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.)
- Pending
Links
- 0 CN(C)C(C=N*)=NC=C Chemical compound CN(C)C(C=N*)=NC=C 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
-
- 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)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A kind of imidazoleimines class part, its nickel complex and its application in polyisoprene synthesis, belong to noval chemical compound and organic synthesis field.Above-mentioned complex is used in polyisoprene synthesis, and step is：Co-catalyst, imidazoleimines nickel complex, isoprene monomer are dissolved into solvent, the 4h of stirring reaction 2, separating-purifying obtain polyisoprene product under argon gas protective condition, under the conditions of 25 DEG C.Polyisoprene synthetic method high-efficiency environment friendly provided by the invention, there is very high selectivity.
Description
Technical field
The present invention relates to noval chemical compound and organic synthesis field.
Background technology
Polyisoprene is a kind of natural Piccopate resin that can be obtained from rubber tree latex separation, and this is also
The main source of natural rubber.Polyisoprene biosynthesis can selectivity two kinds of geometric isomers of generation, Cis formula-Isosorbide-5-Nitraes-
Polyisoprene (coming from the republic of Brazil) and trans-1,4-iroprene polymer (coming from gutta-percha).Have more than 10,000,000 every year
Ton natural elastomer is used for manufacture material such as tire and gloves etc..Rubber tree plantation is only limitted to tropical climate, such as Southeast Asia
And West Africa, grain are greatly developed as agricultural and using soil pollution caused by arsenic class agricultural chemicals, make it have serious region
Political risk.
At present, 15,000,000 tons of synthetic rubber are produced every year.Chemists at present not yet find it is satisfactory and
Practical method produces the geometric configuration of rubber and suitable control double bond, and natural rubber (Cis formulas-Isosorbide-5-Nitrae content is higher than 99%) is still
It is so the preferred material of high-quality rubber, such as aero tyre.Natural rubber is due to high 1,4- microstructure contents (Tg<-65
DEG C) even if also not brittle at low temperature.High Isosorbide-5-Nitrae-microstructure content, as Cis formulas-Isosorbide-5-Nitrae or anti-form-1,4 cause natural rubber
With strain crystallization, the mechanical performance strengthened etc..Therefore, high Cis formulas-Isosorbide-5-Nitrae or anti-form-1, the polymerization of 4 microstructure contents are prepared
Thing is the desirable route for obtaining high performance elastomer.On the other hand, rational 3,4- microstructures content (5-15%) can enter
The further chemical modification of row.In addition, the pendant olefins later stage in polymer is modified or as Polymerization of Ib
Conjugated group provides approach for the exploitation of novel elastomer and low Gas permeable materials.
The industrial production of polyisoprene is concentrated mainly on the anionic polymerisation of isoprene monomer, obtained polymer ratio
Example is the anti-form-1 of Cis formulas -1,4/, 4~5:1.Referring to document, Matyjaszewski and Miiller, Controlled and
Living Polymerizations:From Mechanisms to Applications,WileyVCH,
2009.Catalysts based on rare earth metals such as neodymium afford ratios u p
to 50to 1(1,4-c/s to 1,4-trans).See,e.g.,Zhang et al.,Angew.Chem.Int.Ed.
(2007)46:1909-1913；Zhang et al.,Hou,Angew.Chem.Int.Ed.(2008)47:2642-2645；Gao
and Cui,J.Am.Chem.Soc.(2008)130,4984-4991；Ricci et al.,Coord.Chem.Rev.(2010)
254:661-676；Nishiura and Hou,Nat.Chem.(2010)2:257-268；and Li et al.,
Organometallics(2010)29:2186.
, can only be by digging up mine or obtaining because rare earth metal is expensive, therefore how using more cheaply, be efficiently catalyzed
Agent polymerization 1,3-butadiene, such as isoprene are extremely urgent.It is mainly reflected in Cis formulas -1,4, anti-form-1,4,3,4-, 1,2-
The controllable polymerization of selectivity and molecular weight and molecualr weight distribution and low environmental impact drops.
The content of the invention
To solve the above problems, the present invention provides a kind of imidazoleimines class part, its nickel complex and its in poly- isoamyl two
Application in alkene synthesis, for achieving the above object, technical scheme is as follows：
The present invention provides a kind of imidazoleimines class part, has following structure：
Wherein, R 2,4,6 triphenyl phenyl, t-octyl, 2- sulfidomethyl phenyl, 2- sulfur phenenyl phenyl, 2,6- difluorobenzenes
Base, any one in 2,4,6- trifluorophenyls.
The present invention also provides the nickel complex of above-mentioned part, has following structure：
Wherein, R 2,4,6 triphenyl phenyl, t-octyl, 2- sulfidomethyl phenyl, 2- sulfur phenenyl phenyl, 2,6- difluorobenzenes
Base, any one in 2,4,6- trifluorophenyls.X be Cl, Br in one kind or two kinds, M Ni.
The present invention also provides application of the above-mentioned imidazoleimines nickel complex in polyisoprene synthesis, and step is：It will help
Catalyst, imidazoleimines nickel complex, isoprene monomer are dissolved into solvent, under argon gas protective condition, 0-50 DEG C of condition
Lower stirring reaction 2-4h, terminating reaction, separating-purifying obtain polyisoprene product.
Preferably, the dealkylating reagent additionally added is also included in reaction system, forms three-component catalyze system.
Preferably, the co-catalyst is MAO (MAO), Cl2AlEt、ClAlEt2, SEAC (sesquialter aluminium ethide),
AlEt3In one or two or more kinds.
Preferably, the dealkylating reagent is the one or two or more kinds in aluminate or borate.
Preferably, the borate is the fluorine substituted-phenyl boron (BArF of trityl group (trityl) four or five20)([CPh3][B
(C6F5)4])。
Preferably, in the catalyst system and catalyzing for the dealkylating reagent for not including additionally adding, i.e. two catalytic systems, institute
The mol ratio for stating co-catalyst and imidazoleimines nickel complex is 5:1~1000：1；Isoprene monomer is matched somebody with somebody with imidazoleimines nickel
The mol ratio of compound is 2500:1；The solvent is toluene, hexane, petroleum ether, the one or two or more kinds in dichloromethane, is helped
The concentration of catalyst in a solvent is 0.05-2mol/L.
Preferably, in the catalyst system and catalyzing including dealkylating reagent, i.e., in three-component catalyze system, the co-catalyst with
The mol ratio of imidazoleimines nickel complex is 5:1~1000：1, the mol ratio of isoprene monomer and imidazoleimines nickel complex
For 2500:1, the mol ratio for taking off alkyl reagent and imidazoleimines nickel complex is 1:1~5：1；The solvent is toluene, hexane,
Petroleum ether, the one or two or more kinds in dichloromethane, the concentration of co-catalyst in a solvent is 0.05-2mol/L.
The synthetic method of above-mentioned imidazoleimines class part is as follows：
With imidazoles -2- formaldehyde, all kinds of primary amine are raw material, and a small amount of formic acid is catalyst, is contracted under the conditions of methanol eddy
Reaction is closed, and then synthesizes imidazoleimines class part.Composition principle is as follows：
Wherein, R 2,4,6 triphenyl phenyl, t-octyl, 2- sulfidomethyl phenyl, 2- sulfur phenenyl phenyl, 2,6- difluorobenzenes
Base, any one in 2,4,6- trifluorophenyls.
The synthetic method of above-mentioned imidazoleimines nickel complex is as follows：
With imidazoleimines class part and NiCl2、NiBr2In one kind or two kinds at ambient temperature in dichloromethane or four
With stoichiometric proportion (mol ratio) 1 in hydrogen furans:1 reaction 48h, after reaction terminates, drains solvent, remaining solid is washed with hexane
Wash, dry, obtain imidazoleimines nickel (II) complex.Composition principle is as follows：
Wherein, R 2,4,6 triphenyl phenyl, t-octyl, 2- sulfidomethyl phenyl, 2- sulfur phenenyl phenyl, 2,6- difluorobenzenes
Base, any one in 2,4,6- trifluorophenyls.X be Cl, Br in one kind or two kinds, M Ni.
Application of the above-mentioned complex in polyisoprene synthesis, it is specially：
Do not including additionally adding catalyst system and catalyzing of the borane reagent as dealkylating reagent, i.e. in two catalytic systems,
Comprise the following steps:
(1) co-catalyst, solvent (toluene), imidazoleimines nickel complex are added in Schlenk bottles, then added different
Pentadiene monomer, 2-4h, wherein whole argon gas protection, co-catalyst and imidazoleimines nickel complex are stirred under the conditions of 0-50 DEG C
Mol ratio be 5:1~50：1, the mol ratio of isoprene monomer and imidazoleimines nickel complex is 2500:1.
(2) after the reaction of step (1) terminates, 5mL 1M methanol hydrochloride solution, 25mL methanol, filtering, distilled water are added
Washing, solid is collected, is washed repeatedly with methanol, obtained white solid product is placed in 40 DEG C of vacuum drying chambers and dried, is obtained
To dry white solid product, i.e. polyisoprene.The conversion ratio of gained polyisoprene is 80%-99%, Cis formulas-Isosorbide-5-Nitrae
Selectivity is selective in 90%-98% in 5%-45% or anti-form-1,4 in 55%-95%, 3,4- selectivity.
(3) charging sequence can be changed to co-catalyst, toluene, isoprene monomer being added in step (1)
In Schlenk bottles, imidazoleimines nickel complex is then added, 2-4h, whole argon gas protection, wherein helping are stirred under the conditions of 0-50 DEG C
The mol ratio of catalyst and imidazoleimines nickel complex is 25:1~1000：1, isoprene monomer and imidazoleimines nickel complex
Mol ratio be 2500:1.
Preferably, when doing co-catalyst with MAO, the mol ratio of MAO and imidazoleimines nickel complex is 500 in step (1):
1-1000:1。
Preferably, ClAlEt is used2When doing co-catalyst, ClAlEt in step (1)2With mole of imidazoleimines nickel complex
Than for 100:1-10:1.
Preferably, reaction temperature is 25 DEG C in step (1), and the reaction time is 2 hours.
In the catalyst system and catalyzing including extra addition borane reagent as dealkylating reagent, i.e., in three-component catalyze system, bag
Include following steps:
(1) co-catalyst, toluene, imidazoleimines nickel complex, de- alkyl reagent are added in Schlenk bottles, then
Isoprene monomer is added, 2-4h is stirred under the conditions of 25 DEG C, whole argon gas protection, wherein co-catalyst is matched somebody with somebody with imidazoleimines nickel
The mol ratio of compound is 5:1~50：1, the mol ratio of isoprene monomer and imidazoleimines nickel complex is 2500:1, take off alkyl
The mol ratio of reagent and imidazoleimines nickel complex is 1:1~5：1.
(2) after the reaction of step (1) terminates, 5mL 1M methanol hydrochloride solution, 25mL methanol, filtering, distilled water are added
Washing, solid is collected, is washed repeatedly with methanol, obtained white solid product is placed in 40 DEG C of vacuum drying chambers and dried, is obtained
To dry white solid product, i.e. polyisoprene.The conversion ratio of gained polyisoprene is 80%-99%, Cis formulas-Isosorbide-5-Nitrae
Selectivity is selective in 90%-98% in 5%-45% or anti-form-1,4 in 55%-95%, 3,4- selectivity.
(3) charging sequence can be changed to co-catalyst, toluene, isoprene monomer being added in step (1)
In Schlenk bottles, imidazoleimines nickel complex is then added, 2-4h is stirred under the conditions of 25 DEG C 25, whole argon gas is protected, its
The mol ratio of middle co-catalyst and imidazoleimines nickel complex is 25:1~1000：1, isoprene monomer is matched somebody with somebody with imidazoleimines nickel
The mol ratio of compound is 2500:1.
Preferably, when doing co-catalyst with MAO, the mol ratio of MAO and imidazoleimines nickel complex is 500 in step (1):
1-1000:1。
Preferably, ClAlEt is used2When doing co-catalyst, ClAlEt in step (1)2With mole of imidazoleimines nickel complex
Than for 100:1-10:1.
Preferably, reaction temperature is 25 DEG C in step (1), and the reaction time is 2 hours.
Preferably, it is the fluorine substituted-phenyl boron (BArF of trityl group (trityl) four or five alkyl reagent to be taken off in step (1)20)
[CPh3][B(C6F5)4].
Beneficial effect
The invention provides a kind of new imidazoleimines and its nickel complex, above-mentioned complex provided by the present invention passes through
Initiator, co-catalyst are added, alkylating reagent etc. can obtain homogeneous Ziegler-Natta catalyst and carry out efficient, high selection
Property synthetic polyisoprenes, be high-performance and speciality polymer material exploitation construction method and application.Institute of the present invention
There is provided complex has stronger tolerance air, moisture etc., reduces the requirement to reaction condition, at the same with anionic polymerisation and dilute
Earth metal coordinated anionic polymerization is compared, and present invention reduces production cost, effectively increases the controllable polymerization of polyisoprene,
Make its molecular weight distribution controllable in 2-8, number-average molecular weight is in Mn~1000-106, can be very good to control cis-1,4 selectivity
In 60%-98% or trans-1,4 selectivity>98%.1,2- polymerization control is below 1%, and 3,4- polymerization controls are 40%
Below.High conversion rate is in 95%.Polymerization system provided by the present invention be applicable to biomass isoprene monomer polymerization and
Industrial polymerisation produces.
Embodiment
With reference to specific embodiment, the present invention will be further described, but the present invention should not be limited by the examples.
It is conventional method if the experimental method used in following embodiments is without specified otherwise.
If material, reagent used in following embodiments etc. commercially obtain without specified otherwise.
Experiment material and method
Unless otherwise indicated, all reactions and the operation of Air-sensitive compounds are entered under standard noble gas atmosphere (Ar)
OK.The storage of all glasswares uses in an oven or after being dried before use with flame and after logical argon atmosphere.Without water-soluble
The purifying of agent is with reference to purified reagent handbook CH2Cl2(CaH2Backflow, distillation), toluene (Na flows back, distillation), tetrahydrofuran, ether
(Na, benzophenone are back to purple, distillation), n-hexane, acetonitrile (CaH2Backflow, distillation).Thin-layer chromatography (TLC)
Carried out in advance with the EMD TLC plates of 250 μ m thick silica gel 60 (40-63 μm) F254 pre-coatings, by purple
Fluorescent quenching under outer light (Uv) shows plate, and flash chromatography is carried out on Silicycle silica gel 60 (40-63 μm) in 0.3-
Elution is used under 0.5bar pressure.Yield refers to the specpure compound of the separation of purifying.Recorded on Bruker1H NMR (600MHz or 400MHz) and13C NMR (150MHz or 100MHz) are composed.
1H NMR and13C NMR are used for determining the selectivity in polymerisation, and its relaxation time is respectively 10 seconds and 5 seconds.
CDCl3Handled by alkali alumina.CD2Cl2By the methods of degassing-freezing-degassing and passing throughMolecular sieve drying.Chemistry
Displacement using tetramethylsilane be internal standard as refer to (ppm).Chemical shift of the deuterium with solvent be：For1H NMR：CDCl3=
7.26ppm CD2Cl2：5.32ppm.For13C NMR：CDCl3=77.16ppm, CD2Cl2=53.80ppm.Data report is such as
Under：Chemical shift, multiplicity (s=is unimodal, and d=is bimodal, t=triplets, q=quartets, m=multiplets, and br=is wide), coupling
Constant is in units of Hz.For paramagnetic molecule,1H NMR and13C NMR datas are to report chemical shift, followed by half height
Peak width, unit Hz.The molal weight of polyisoprene uses the size exclusion chromatography of the Varian GPC equipped with a set of 3 post
Method and RI detectors measure.Using THF as eluent, polystyrene is as standard items.SEC chromatographic datas are reported to divide equally again
Son amount (Mw) (g/mol) and polydispersity (D).
Reagent：Reagent comes from commercial prod (Aldrich, Strem, Alfa Aesar or TCI), unless otherwise saying
It is bright, directly used after purchase.2- pyridine carboxaldehydes (Aldrich, 98%) are using preceding being distilled.T-octanylamine (Aldrich,
97%) using preceding being distilled.Use iron chloride (II) (99.999%Strem).Trityl four (pentafluorophenyl group) boric acid
Salt (glassy yellow powder, 98%, Strem).Isoprene (99%, Alfa Aesar or TCI) passes through CaH2Steam again.Trimethyl
Aluminium, triethyl aluminum and three-aluminium isobutyl buy (purity 95%) respectively in the metal can from Aldrich.Trialkylaluminium alkane
Base reagent can shift or distill into holding vessel preservation by cannula, and (both storing modes are not observed mainly
Difference).
The preparation of the imidazoleimines class part of embodiment 1
All parts described herein are obtained by substituted aldehydes or ketones and primary amine condensation reaction.Complicated amine needs to close in advance
Into.The amine of many commercializations and the aldehyde and ketone of substitution can carry out one-step synthesis part (imines condensation).
(1) imidazoleimines class ligand compound a synthesis
Ar protection under, successively into 25mL two-mouth bottle add dissolved with 1- methyl-imidazoles -2- formaldehyde (275.3mg,
2.5mmol, 1eq.) methanol solution 10mL, t-octanylamine (0.48mL, 3mmol, 1.2eq.), formic acid (0.1mL), 80 DEG C are next time
Stream reaction, TLC tracing detections are until 1- methyl-imidazoles -2- formaldehyde raw materials disappear.Solvent is spin-dried for, is evaporated under reduced pressure and removes unreacted
Raw material t-octanylamine, remaining light red liquid is target product, yield 66%.
(2) imidazoleimines class ligand compound b synthesis
2,4,6- triphenyls aniline (963.6mg, 3mmol, 1.2eq.) is added into 25mL two-mouth bottle, three are replaced with Ar
It is secondary, add the methanol solution 10mL dissolved with 1- methyl-imidazoles -2- formaldehyde (275.3mg, 2.5mmol, 1eq.), formic acid
(0.1mL), back flow reaction at 80 DEG C, TLC tracing detections are until 1- methyl-imidazoles -2- formaldehyde raw materials disappear.Solvent is spin-dried for, is used
40mL n-hexanes recrystallize 5 times, obtain yellow solid 413.2mg, yield 40%.
The synthesis of the imidazoleimines nickel complex of embodiment 2
(1) imidazoleimines nickel complex c synthesis
In glove box, anhydrous NiCl is added into 10mL Schlenk pipes2(73.9mg, 0.57mmol, 1eq.), it is real
The imidazoleimines class ligand compound a (72.3mg, 0.57mmol, 1eq.) of the preparation of example 1 is applied, adds 5mL anhydrous DCM, room
The lower stirring of temperature 4 days.After question response terminates, it will separate out solid dissolving with the anhydrous DCM of 10mL × 2 and filter, collect DCM phases and obtain
Orange liquid, remaining DCM is drained, washed twice with 20mL anhydrous n-hexane, removed supernatant and dry residue, obtain
To brown solid, yield 62%.
(2) imidazoleimines nickel complex d synthesis
In glove box, anhydrous NiBr is added into 10mL Schlenk pipes2(126.7mg, 0.58mmol, 1eq.), it is real
The imidazoleimines class ligand compound a (75.4mg, 0.58mmol, 1eq.) of the preparation of example 1 is applied, adds 5mL anhydrous THF, room
The lower stirring of temperature 4 days.After question response terminates, remaining THF is drained, by the solid dissolving of precipitation and is divided with the anhydrous DCM of 10mL × 2
Do not filter, drain remaining DCM, washed twice with 20mL anhydrous n-hexane, remove supernatant and dry residue, obtain
Light green solid, yield 71%.
(3) imidazoleimines nickel complex e synthesis
In glove box, anhydrous NiCl is added into 10mL Schlenk pipes2(41.5mg, 0.32mmol, 1eq.), it is real
The imidazoleimines class ligand compound b (130.0mg, 0.32mmol, 1eq.) of the preparation of example 1 is applied, adds 5mL anhydrous DCM, room
The lower stirring of temperature 2 days.After question response terminates, it will separate out solid dissolving with the anhydrous DCM of 10mL × 2 and filter respectively, obtain orange red
Color liquid, drain remaining DCM；Washed twice again with 20mL anhydrous n-hexane, remove supernatant and dry residue, obtain
To brown solid, yield 59%.
(4) imidazoleimines nickel complex f synthesis
In glove box, anhydrous NiBr is added into 10mL Schlenk pipes2(69.9mg, 0.32mmol, 1eq.), it is real
The imidazoleimines class ligand compound b (132.0mg, 0.32mmol, 1eq.) of the preparation of example 1 is applied, adds 5mL anhydrous THF, room
The lower stirring of temperature 2 days.After question response terminates, will reaction extraction raffinate filtering, obtain cyan coloured liquid, remaining THF drained, with 10mL ×
2 anhydrous DCM will separate out solid dissolving and filter respectively, drain remaining DCM；Washed twice with 20mL anhydrous n-hexane,
Remove supernatant and dry residue, obtain light green solid, yield 49%.
In polymerisation catalyst system and catalyzing, the research is divided into two component catalyst systems and three-component catalyze system, below will knot
Closing specific implementation case, the present invention will be further described.
It is catalyzed isoprene polymerization double-component catalyst system
Embodiment 3
A 25mL Schlenk bottle is taken, sequentially adds co-catalyst MAO (4mmol, 500eq.), toluene 5mL thereto,
Complex c (8 μm of ol, 1eq.) is dissolved in 1mL dichloromethane, and 2min is stirred at room temperature in the mixed liquor, then adds isoamyl
Diene monomers (20mmol, 2500eq.), after polymerisation carries out 2h at 25 DEG C, add 1M methanol hydrochloride solution terminating reaction.
Sticky polymer solution is poured into 50mL ethanol, settles polymer.The polymer after clear liquid is outwelled, successively with steaming
Distilled water, ethanol washing, resulting polymers are placed in 40 DEG C of vacuum drying chambers and dried to constant weight, obtain product polyisoprene, produce
Rate 80%.Reaction selectivity is the 3,4- polyisoprene containing 89.7% trans-1,4 and 10.3%.
Embodiment 4
A 25mL Schlenk bottle is taken, sequentially adds co-catalyst ClAlEt thereto2(4mmol, 500eq.), toluene
5mL, complex d (8 μm of ol, 1eq.) are dissolved in 1mL dichloromethane, and 2min is stirred at room temperature in the mixed liquor, then adds
Isoprene monomer (20mmol, 2500eq.), after polymerisation carries out 2h at 25 DEG C, the methanol hydrochloride solution for adding 1M terminates
Reaction.Sticky polymer solution is poured into 50mL ethanol, settles polymer.The polymer after clear liquid is outwelled, according to
Secondary to be washed with distilled water, ethanol, resulting polymers are placed in 40 DEG C of vacuum drying chambers and dried to constant weight, obtain the poly- isoamyl two of product
Alkene, yield 85%.Reaction selectivity is the 3,4- polyisoprene containing 67.0% cis-1,4 and 33.0%.
Embodiment 5
A 25mL Schlenk bottle is taken, sequentially adds co-catalyst ClAlEt thereto2(4mmol, 500eq.), toluene
5mL, complex e (8 μm of ol, 1eq.) are dissolved in 1mL dichloromethane, and 2min is stirred at room temperature in the mixed liquor, then adds
Isoprene monomer (20mmol, 2500eq.), after polymerisation carries out 2h at 25 DEG C, the methanol hydrochloride solution for adding 1M terminates
Reaction.Sticky polymer solution is poured into 50mL ethanol, settles polymer.The polymer after clear liquid is outwelled, according to
Secondary to be washed with distilled water, ethanol, resulting polymers are placed in 40 DEG C of vacuum drying chambers and dried to constant weight, obtain the poly- isoamyl two of product
Alkene, yield 81%.Reaction selectivity is the 3,4- polyisoprene containing 66.0% cis-1,4 and 34.0%.
Embodiment 6
A 25mL Schlenk bottle is taken, sequentially adds co-catalyst ClAlEt thereto2(4mmol, 500eq.), toluene
5mL, complex f (8 μm of ol, 1eq.) are dissolved in 1mL dichloromethane, and 2min is stirred at room temperature in the mixed liquor, then adds
Isoprene monomer (20mmol, 2500eq.), after polymerisation carries out 2h at 25 DEG C, the methanol hydrochloride solution for adding 1M terminates
Reaction.Sticky polymer solution is poured into 50mL ethanol, settles polymer.The polymer after clear liquid is outwelled, according to
Secondary to be washed with distilled water, ethanol, resulting polymers are placed in 40 DEG C of vacuum drying chambers and dried to constant weight, obtain the poly- isoamyl two of product
Alkene, yield 90%.Reaction selectivity is the 3,4- polyisoprene containing 69.0% cis-1,4 and 31.0%.
Embodiment 7
A 25mL Schlenk bottle is taken, sequentially adds co-catalyst Cl thereto2AlEt (4mmol, 500eq.), toluene
5mL, complex c (8 μm of ol, 1eq.) are dissolved in 1mL dichloromethane, and 2min is stirred at room temperature in the mixed liquor, then adds
Isoprene monomer (20mmol, 2500eq.), after polymerisation carries out 2h at 25 DEG C, the methanol hydrochloride solution for adding 1M terminates
Reaction.Sticky polymer solution is poured into 50mL ethanol, settles polymer.The polymer after clear liquid is outwelled, according to
Secondary to be washed with distilled water, ethanol, resulting polymers are placed in 40 DEG C of vacuum drying chambers and dried to constant weight, obtain the poly- isoamyl two of product
Alkene, yield 99%, reaction selectivity are to contain 99.0% trans-1,4- polyisoprene and cyclisation or cross-linking products.
Embodiment 8
A 25mLSchlenk bottle is taken, sequentially adds co-catalyst Cl thereto2AlEt (4mmol, 500eq.), toluene
5mL, complex e (8 μm of ol, 1eq.) are dissolved in 1mL dichloromethane, and 2min is stirred at room temperature in the mixed liquor, then adds
Isoprene monomer (20mmol, 2500eq.), after polymerisation carries out 2h at 25 DEG C, the methanol hydrochloride solution for adding 1M terminates
Reaction.Sticky polymer solution is poured into 50mL ethanol, settles polymer.The polymer after clear liquid is outwelled, according to
Secondary to be washed with distilled water, ethanol, resulting polymers are placed in 40 DEG C of vacuum drying chambers and dried to constant weight, obtain the poly- isoamyl two of product
Alkene, yield 99%, reaction selectivity are to contain 99.0% trans-1,4- polyisoprene and cyclisation or cross-linking products.
It is catalyzed the component catalyst system of isoprene polymerization three
Embodiment 9
A 25mL Schlenk bottle is taken, sequentially adds co-catalyst ClAlEt thereto2(0.2mmol, 25eq.), first
Benzene 5mL, complex c (8 μm of ol, 1eq.), [CPh3][B(C6F5)4] (8 μm of ol, 1eq.) is dissolved in 1mL dichloromethane, this is mixed
Close liquid and 2min is stirred at room temperature, then add isoprene monomer (20mmol, 2500eq.), polymerisation is carried out at 25 DEG C
After 2h, 1M methanol hydrochloride solution terminating reaction is added.Sticky polymer solution is poured into 50mL ethanol, polymer is sunk
Drop comes out.The polymer after clear liquid is outwelled, is washed successively with distilled water, ethanol, resulting polymers are placed in 40 DEG C of vacuum drying chambers
Middle drying obtains product polyisoprene, yield 58% to constant weight.Reaction selectivity be containing 72.0% cis-1,4 and
28.0% 3,4- polyisoprene.
Embodiment 10
A 25mL Schlenk bottle is taken, sequentially adds co-catalyst ClAlEt thereto2(0.2mmol, 25eq.), first
Benzene 5mL, complex d (8 μm of ol, 1eq.), [CPh3][B(C6F5)4] (8 μm of ol, 1eq.) is dissolved in 1mL dichloromethane, this is mixed
Close liquid and 2min is stirred at room temperature, then add isoprene monomer (20mmol, 2500eq.), polymerisation is carried out at 25 DEG C
After 2h, 1M methanol hydrochloride solution terminating reaction is added.Sticky polymer solution is poured into 50mL ethanol, polymer is sunk
Drop comes out.The polymer after clear liquid is outwelled, is washed successively with distilled water, ethanol, resulting polymers are placed in 40 DEG C of vacuum drying chambers
Middle drying obtains product polyisoprene, yield 52% to constant weight.Reaction selectivity be containing 74.0% cis-1,4 and
26.0% 3,4- polyisoprene.
Embodiment 11
A 25mL Schlenk bottle is taken, sequentially adds co-catalyst ClAlEt thereto2(0.2mmol, 500eq.), first
Benzene 5mL, complex e (8 μm of ol, 1eq.), [CPh3][B(C6F5)4] (8 μm of ol, 1eq.) is dissolved in 1mL dichloromethane, this is mixed
Close liquid and 2min is stirred at room temperature, then add isoprene monomer (20mmol, 2500eq.), polymerisation is carried out at 25 DEG C
After 2h, 1M methanol hydrochloride solution terminating reaction is added.Sticky polymer solution is poured into 50mL ethanol, polymer is sunk
Drop comes out.The polymer after clear liquid is outwelled, is washed successively with distilled water, ethanol, resulting polymers are placed in 40 DEG C of vacuum drying chambers
Middle drying obtains product polyisoprene, yield 70% to constant weight.Reaction selectivity be containing 72.0% cis-1,4 and
28.0% 3,4- polyisoprene.
Embodiment 12
A 25mL Schlenk bottle is taken, sequentially adds co-catalyst ClAlEt thereto2(0.2mmol, 500eq.), first
Benzene 5mL, complex f (8 μm of ol, 1eq.), [CPh3][B(C6F5)4] (8 μm of ol, 1eq.) is dissolved in 1mL dichloromethane, this is mixed
Close liquid and 2min is stirred at room temperature, then add isoprene monomer (20mmol, 2500eq.), polymerisation is carried out at 25 DEG C
After 2h, 1M methanol hydrochloride solution terminating reaction is added.Sticky polymer solution is poured into 50mL ethanol, polymer is sunk
Drop comes out.The polymer after clear liquid is outwelled, is washed successively with distilled water, ethanol, resulting polymers are placed in 40 DEG C of vacuum drying chambers
Middle drying obtains product polyisoprene, yield 72% to constant weight.Reaction selectivity be containing 71.0% cis-1,4 and
29.0% 3,4- polyisoprene.
Embodiment 13
A 25mL Schlenk bottle is taken, sequentially adds co-catalyst Cl thereto2AlEt (0.2mmol, 500eq.), first
Benzene 5mL, complex c (8 μm of ol, 1eq.), [CPh3][B(C6F5)4] (8 μm of ol, 1eq.) is dissolved in 1mL dichloromethane, this is mixed
Close liquid and 2min is stirred at room temperature, then add isoprene monomer (20mmol, 2500eq.), polymerisation is carried out at 25 DEG C
After 2h, 1M methanol hydrochloride solution terminating reaction is added.Sticky polymer solution is poured into 50mL ethanol, polymer is sunk
Drop comes out.The polymer after clear liquid is outwelled, is washed successively with distilled water, ethanol, resulting polymers are placed in 40 DEG C of vacuum drying chambers
Middle drying obtains product polyisoprene, yield 63% to constant weight.Reaction selectivity be containing 70.0% cis-1,4 and
30.0% 3,4- polyisoprene.
Embodiment 14
A 25mL Schlenk bottle is taken, sequentially adds co-catalyst Cl thereto2AlEt (0.2mmol, 500eq.), first
Benzene 5mL, complex e (8 μm of ol, 1eq.), [CPh3][B(C6F5)4] (8 μm of ol, 1eq.) is dissolved in 1mL dichloromethane, this is mixed
Close liquid and 2min is stirred at room temperature, then add isoprene monomer (20mmol, 2500eq.), polymerisation is carried out at 25 DEG C
After 2h, 1M methanol hydrochloride solution terminating reaction is added.Sticky polymer solution is poured into 50mL ethanol, polymer is sunk
Drop comes out.The polymer after clear liquid is outwelled, is washed successively with distilled water, ethanol, resulting polymers are placed in 40 DEG C of vacuum drying chambers
Middle drying obtains product polyisoprene, yield 54% to constant weight.Reaction selectivity be containing 74.0% cis-1,4 and
26.0% 3,4- polyisoprene.
Claims (9)
1. a kind of imidazoleimines class part, it is characterised in that there is following structure：
Wherein, R 2,4,6 triphenyl phenyl, t-octyl, sulfur-bearing substituent aryl, 2,6- difluorophenyls, 2,4,6- trifluorophenyls
In any one.
2. a kind of imidazoleimines nickel complex, it is characterised in that there is following structure：
Wherein, R 2,4,6 triphenyl phenyl, t-octyl, sulfur-bearing substituent aryl, 2,6- difluorophenyls, 2,4,6- trifluorophenyls
In any one, one kind in X Cl, Br or two kinds, M Ni.
3. application of the imidazoleimines nickel complex in polyisoprene synthesis described in claim 2, it is characterised in that：Step
For：Co-catalyst, imidazoleimines nickel complex, isoprene monomer are dissolved into solvent, under argon gas protective condition, 0-50
Stirring reaction 2-4h under the conditions of DEG C, separating-purifying obtain polyisoprene product.
4. application according to claim 3, it is characterised in that：Also include dealkylating reagent in reaction system.
5. the application according to claim 3 or 4, it is characterised in that：The co-catalyst be MAO (MAO),
Cl2AlEt、ClAlEt2, SEAC (sesquialter aluminium ethide), AlEt3In one or two or more kinds.
6. application according to claim 4, it is characterised in that：The dealkylating reagent is in aluminate or borate
It is one or two or more kinds of.
7. application according to claim 6, it is characterised in that：The borate is the fluorine of trityl group (trityl) four or five
Substituted-phenyl boron (BArF20)([CPh3][B(C6F5)4])。
8. application according to claim 3, it is characterised in that：Mole of the co-catalyst and imidazoleimines nickel complex
Than for 5:1~1000：1；The mol ratio of isoprene monomer and imidazoleimines nickel complex is 2500:1；The solvent is first
Benzene, hexane, petroleum ether, the one or two or more kinds in dichloromethane, the concentration of co-catalyst in a solvent is 0.05-2mol/
L。
9. application according to claim 4, it is characterised in that：Mole of the co-catalyst and imidazoleimines nickel complex
Than for 5:1~1000：1, the mol ratio of isoprene monomer and imidazoleimines nickel complex is 2500:1, take off alkyl reagent and miaow
The mol ratio of azoles imine nickel complex is 1:1~5：1；The solvent is toluene, hexane, petroleum ether, one kind in dichloromethane
Or more than two kinds, the concentration of co-catalyst in a solvent is 0.05-2mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710877522.3A CN107522660A (en) | 2017-09-26 | 2017-09-26 | Imidazoleimines class part, its nickel complex and its application in polyisoprene synthesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710877522.3A CN107522660A (en) | 2017-09-26 | 2017-09-26 | Imidazoleimines class part, its nickel complex and its application in polyisoprene synthesis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107522660A true CN107522660A (en) | 2017-12-29 |
Family
ID=60736194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710877522.3A Pending CN107522660A (en) | 2017-09-26 | 2017-09-26 | Imidazoleimines class part, its nickel complex and its application in polyisoprene synthesis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107522660A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586641A (en) * | 2018-04-28 | 2018-09-28 | 中国科学院青岛生物能源与过程研究所 | A kind of high-efficient iron-series catalyst and the preparation method and application thereof of catalysis isoprene polymerization |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193828A (en) * | 2013-04-03 | 2013-07-10 | 西北大学 | Double-imidazole imide nickel hydroxide coordination complex as well as preparation method and application thereof |
| US20140011971A1 (en) * | 2011-02-08 | 2014-01-09 | President And Fellows Of Harvard College | Iron complexes and methods for polymerization |
| CN105503763A (en) * | 2014-10-17 | 2016-04-20 | 中国科学院上海有机化学研究所 | Novel polyolefin oil catalyst and applications thereof |
-
2017
- 2017-09-26 CN CN201710877522.3A patent/CN107522660A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140011971A1 (en) * | 2011-02-08 | 2014-01-09 | President And Fellows Of Harvard College | Iron complexes and methods for polymerization |
| CN103193828A (en) * | 2013-04-03 | 2013-07-10 | 西北大学 | Double-imidazole imide nickel hydroxide coordination complex as well as preparation method and application thereof |
| CN105503763A (en) * | 2014-10-17 | 2016-04-20 | 中国科学院上海有机化学研究所 | Novel polyolefin oil catalyst and applications thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586641A (en) * | 2018-04-28 | 2018-09-28 | 中国科学院青岛生物能源与过程研究所 | A kind of high-efficient iron-series catalyst and the preparation method and application thereof of catalysis isoprene polymerization |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108530571B (en) | Iron-based alkylpyridinylimine catalyst and preparation method and application thereof | |
| CN110452272B (en) | Bipyridine iron complex, preparation method thereof and application thereof in conjugated diene polymerization | |
| CN109952325B (en) | Process for preparing syndiotactic 1, 2-polybutadiene in the presence of a catalytic system comprising a pyridyliron complex | |
| Bonnet et al. | Tuning the catalytic properties of rare earth borohydrides for the polymerisation of isoprene | |
| CN108586641A (en) | A kind of high-efficient iron-series catalyst and the preparation method and application thereof of catalysis isoprene polymerization | |
| Jing et al. | Synthesis and characterization of aminopyridine iron (II) chloride catalysts for isoprene polymerization: Sterically controlled monomer enchainment | |
| CN109942638A (en) | Asymmetric alpha-diimine nickel (II) complex that methylbenzyl is replaced containing ortho position two for vinyl polymerization | |
| CN109134730B (en) | Aryl substituted pyridylamine iron catalyst, and preparation method and application thereof | |
| CN105037588B (en) | A kind of iso-indoles rare-earth metal catalyst, preparation method and application | |
| CN102659961B (en) | Cobalt catalyst and application thereof in 1,3-butadiene polymerization reaction | |
| CN109851700A (en) | A kind of trident pyridinimine 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 | |
| CN108658850A (en) | A kind of fluorine-containing pyridine imine class ligand, its transient metal complex and its application in polyisoprene synthesis | |
| CN108641026B (en) | Application of benzyl imine pyridine iron complex in preparation of isoprene rubber | |
| CN107522660A (en) | Imidazoleimines class part, its nickel complex and its application in polyisoprene synthesis | |
| CN108484809B (en) | Olefin polymerization catalyst | |
| CN108659055A (en) | A kind of iron complex, preparation method and its application in isoprene polymerization based on flexible back bone | |
| 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 | |
| CN107556246A (en) | Imidazoleimines class part, its iron/cobalt complex and its application in polyisoprene synthesis | |
| CN104592425B (en) | A kind of cycloheptatriene base rare-earth metal catalyst, preparation method and application | |
| CN103554365B (en) | One class is based on rare-earth catalysis system butadiene-isoprene copolymer and preparation method thereof | |
| Diether et al. | Rare-earth metal-promoted (double) C–H-bond activation of a lutidinyl-functionalized alkoxy ligand: formation of [ONC] pincer-type ligands and implications for isoprene polymerization | |
| CN102127116B (en) | Caliper type chromium complex and preparation method and application thereof | |
| CN113731505A (en) | Ethylene oligomerization catalyst system and application |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20171229 |
|
| WD01 | Invention patent application deemed withdrawn after publication |