CN102633840B - Clamp-type iron complex and preparation method and application thereof - Google Patents
Clamp-type iron complex and preparation method and application thereof Download PDFInfo
- Publication number
- CN102633840B CN102633840B CN201210096766.5A CN201210096766A CN102633840B CN 102633840 B CN102633840 B CN 102633840B CN 201210096766 A CN201210096766 A CN 201210096766A CN 102633840 B CN102633840 B CN 102633840B
- Authority
- CN
- China
- Prior art keywords
- title complex
- bis
- bromobenzene
- iron complex
- sections title
- 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.)
- Expired - Fee Related
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a clamp-type iron complex and a preparation method and application thereof, and belongs to the field of catalysis technologies. The clamp-type iron complex is based on [NCN]-coordination. The preparation method comprises the following steps of: adding a butyl lithium solution into a ligand solution under the condition of the temperature of -78 to -40 DEG C, and reacting to obtain a reaction solution; adding ferrous chloride into the reaction solution, naturally raising the temperature to room temperature, and continuing reaction; and adding hexane to perform filtration and recrystallization. A catalyst consisting of the [NCN]-coordination clamp-type iron complex and alkyl aluminum is used for catalyzing butadiene syn-1,4 to perform selective polymerization. The clamp-type iron complex is convenient to prepare and high in stability; during selective polymerization of the butadiene under the catalyst, the using amount of the catalyst is small, the polymerization reaction speed is high, the conversion efficiency is high, and syn-1,4 selectivity is relatively high, and polymer molecule weight and molecule weight distribution are controllable; the system formed by the catalyst is homogeneous; the clamp-type iron complex is convenient to use; during polymerization, the temperature fluctuation range is small; and the reaction is easy to control.
Description
Technical field
The invention belongs to the field of catalysis technique, particularly a kind of based on [NCN]
-the pincers sections title complex of coordination, synthetic method and at divinyl along the application in Isosorbide-5-Nitrae-selective polymerisation.
Background technology
At present, polyolefine material become in synthetic resins that output is maximum, purposes the most a kind of polymer starting material.Wherein, polyhutadiene and polyisoprene are important synthetic rubber kinds.Polybutadiene rubber is the second largest general synthesized polymer material in the world that is only second to styrene-butadiene rubber(SBR).There is excellent spring, strong wear resistance, resistance to low temperature, heat-dissipating is low, hysteresis loss is little, flexible resistance, resistance to cracking and the advantage such as dynamic property is good, can compare favourably with natural rubber, chloroprene rubber and paracril etc., in the production of the rubber items such as doughnut, adhesive tape, emulsion tube and rubber boot, have a wide range of applications.Polyisoprene rubber has good virgin rubber intensity, basic viscosity, ageing resistance and rebound performance, can replace natural rubber to be applied to produce the materials such as doughnut, sebific duct, sponge, sizing agent, conveying belt, medical adhesive.2009, the aggregate consumption of world's polyisoprene was about 540,000 tons, predicted that world consumption amount in 2012 always will reach 640,000 tons of left and right.China has become the consumption big country of polyhutadiene and polyisoprene rubber at present, but throughput can not meet growing consumer need, still needs import.This just requires China must faster production paces and improve technical level, and wherein emphasis is researched and developed efficient catalyst exactly.
Existing serial patent discloses the catalyzer that can be used for divinyl selective polymerisation in recent years, as the patent of invention of the patent of invention of application number 200710056309.2, application number 200810050666.2 has all been introduced the rare earth catalyst that can be used for divinyl selective polymerisation; But the catalyzer that these patents are reported is not to use expensive rare earth element, will use expensive boron additive exactly, and be difficult for preparation.
Summary of the invention
The technical problem to be solved in the present invention is that [NCN] is provided
-pincers sections title complex of coordination and preparation method thereof; And by [NCN]
-pincers sections title complex and the aluminum alkyls of coordination are made catalyzer, for Butadiene along Isosorbide-5-Nitrae-selective polymerisation.Pincers sections composition catalyst provided by the invention is easy to prepare, and raw material is easy to get, and does not need boron additive.
For realizing object of the present invention, provide concrete technical scheme as follows.
A pincers sections title complex is based on [NCN]
-the pincers sections title complex of coordination, has following structure:
Wherein, R
1for the substituting group on skeleton phenyl ring, can be hydrogen, methyl, ethyl, sec.-propyl, fluorine, chlorine, bromine, iodine, the tertiary butyl or trimethyl silicon based etc. but be not limited only to this; R
2for the substituting group on imines carbon, can be methyl, ethyl, sec.-propyl, the tertiary butyl, phenyl or hydrogen etc. but be not limited only to this; R
3for methyl, ethyl, sec.-propyl, the tertiary butyl, hydrogen, methoxyl group, fluorine, chlorine, bromine or iodine etc. but be not limited only to this; R
4for methyl, ethyl, sec.-propyl, the tertiary butyl or hydrogen etc. but be not limited only to this.X is halogen anion, is F
-, Cl
-, Br
-or I
-, preferred Cl
-.
By above-mentioned based on [NCN]
-the pincers sections title complex of coordination, preferably has pincerlike iron complex 1～10, concrete:
Pincerlike iron complex 1:R
1=H, R
2=H, R
3=H, R
4=H, X=Cl;
Pincerlike iron complex 2:R
1=H, R
2=H, R
3=Me, R
4=H, X=Cl;
Pincerlike iron complex 3:R
1=H, R
2=H, R
3=Et, R
4=H, X=Cl;
Pincerlike iron complex 4:R
1=H, R
2=H, R
3=
tbu, R
4=H, X=Cl;
Pincerlike iron complex 5:R
1=H, R
2=H, R
3=
ipr, R
4=H, X=Cl;
Pincerlike iron complex 6:R
1=H, R
2=H, R
3=Me, R
4=Me, X=Cl;
Pincerlike iron complex 7:R
1=H, R
2=H, R
3=Et, R
4=Me, X=Cl;
Pincerlike iron complex 8:R
1=H, R
2=H, R
3=
ipr, R
4=Me, X=Cl;
Pincerlike iron complex 9:R
1=Me, R
2=Me, R
3=OCH
3, R
4=Me, X=Cl;
Pincerlike iron complex 10:R
1=Me, R
2=Ph, R
3=Cl, R
4=Me, X=Cl.
R more preferably
1hydrogen, R
2hydrogen, R
3sec.-propyl, R
4hydrogen.
Clamp a preparation method for sections title complex, its reaction scheme is as follows:
Concrete preparation process and condition be, under-78 ℃～-40 ℃ conditions, the hexane solution of butyllithium is added in the tetrahydrofuran solution of part, and the molar ratio of butyllithium and part is 1.1～1: 1, reacts and within 0.5～1 hour, obtains reaction solution, by the tetrahydrofuran (THF) adducts (FeCl of ferrous chloride or ferrous chloride
2)
2(THF)
3powder join in reaction solution, be naturally warming up to room temperature and continue again to react 4～5 hours, the molar ratio of ferrous chloride and part is 1.2～1: 1, after reaction solution is concentrated after reaction finishes, add hexane, filtration and recrystallization obtains pincerlike iron complex, described part is: 2, 6-bis-(N-phenyl) imido grpup bromobenzene, 2, 6-bis-(N-2, 6-3,5-dimethylphenyl) imido grpup bromobenzene, 2, 6-bis-(N-2, 6-diethyl phenyl) imido grpup bromobenzene, 2, 6-bis-(N-2, 6-di-tert-butyl-phenyl) imido grpup bromobenzene, 2, 6-bis-(N-2, 6-diisopropyl phenyl) imido grpup bromobenzene, 2, 6-bis-(N-2, 4, 6-, trimethylphenyl) imido grpup bromobenzene, 2, 6-bis-(N-4-methyl-2, 6-diethyl phenyl) imido grpup bromobenzene, 2, 6-bis-(N-4-methyl-2, 6-di-t-butyl base phenyl) imido grpup bromobenzene, 2, 6-bis-[(2, 6-dimethoxy-4 '-aminomethyl phenyl) acetylimino]-4-methyl bromobenzene, 2, 6-bis-[(2, the chloro-4-methyl of 6-bis-) benzoylimino base]-4-methyl bromobenzene or 2, 6-bis-[(2, the chloro-4-bromo of 6-bis-) benzoylimino base]-4-bromine bromobenzene etc. but be not limited only to this.
The concentration of the hexane solution of butyllithium is 1.0～2.0mol/L preferably; The concentration of the tetrahydrofuran solution of part has no significant effect preparing iron complex.
A kind of based on [NCN]
-the purposes of the pincers sections title complex of coordination, by [NCN]
-the pincers sections title complex of coordination, aluminum alkyls form catalyzer, for Butadiene along Isosorbide-5-Nitrae-selective polymerisation; Described aluminum alkyls is: AlMe
3, AlEt
3, Al (
ibu)
3or AlEt
2cl, preferably AlMe
3; Aluminum alkyls with based on [NCN]
-the ratio of the pincers sections title complex of coordination is 10～50: 1, preferably 25: 1.
Butadiene is as follows along step and the condition of Isosorbide-5-Nitrae-selective polymerisation:
Measure based on [NCN]
-toluene or the chlorobenzene solution of the pincers sections title complex of coordination are placed in reactor, add aluminum alkyls, stir 5 minutes; Add by mol 500～5000 times to the divinylic monomer of pincers sections title complex, polyreaction is carried out 0.25～18 hour at-40～40 ℃; Add hydrochloric acid and the ethanolic soln of the 2,6 di tert butyl 4 methyl phenol (BHT) that contains by mass 1% to stop polymerization; Pouring reactant in ethanol sedimentation and go out polymkeric substance, is white solid product.
Polymerization gained white solid product is placed in to vacuum drying oven, at 40 ℃, is dried 48 hours.The molecular weight of polyhutadiene is measured with gel permeation chromatograph, and the microstructure content of polyhutadiene calculates with NMR (Nuclear Magnetic Resonance) spectrum or infrared spectra.
In the hydrochloric acid and ethanolic soln of the BHT of termination polymerization, the volume ratio of hydrochloric acid and ethanol can be 1: 8～10.
Polyreaction can be carried out in the liquid that catalyst system is had no adverse effect.This class I liquid I comprises pentane, hexane, heptane, octane, hexanaphthene, methylcyclohexane, toluene, dimethylbenzene, chlorobenzene or mixed alkanes or BTX aromatics or mix the common solvent such as halohydrocarbon but be not limited in this, preferably toluene, or chlorobenzene.Polymeric reaction temperature can change in very wide scope, and typical temperature range is-40 ℃～40 ℃, and preferred scope is-20 ℃～20 ℃.Polymerization time is 30 minutes to 18 hours.
Pincers sections title complex of the present invention, this type of pincers sections compound is easy to prepare, and good stability, can preserve under normal temperature and not decompose for 20 days, still has catalytic activity.These pincerlike iron complexes are alternative Butadiene Polymerization under aluminum alkyls exists, promotor consumption low (10～50 times), and do not need expensive boron additive, polymerization rate fast (30 minutes to 18 hours), transformation efficiency high (40.2%～83.2%), polymericular weight (1.67 ten thousand～116.0 ten thousand) and molecular weight distribution (1.99～7.15) are all controlled, have good cis-Isosorbide-5-Nitrae selectivity.The system that catalyzer forms is homogeneous phase, easy to use, and catalytic performance is stable, and in polymerization process, temperature fluctuation range is little, and reaction is easily controlled.
Embodiment
Following examples 1～10th, the embodiment of pincers sections complex structure and preparation, reactant wherein (raw material) discloses structure and preparation method's compound or the compound of preparing by existing method for document.Ferrous chloride in embodiment also can be with the tetrahydrofuran (THF) adducts (FeCl of the ferrous chloride that contains equimolar ferro element
2)
2(THF)
3replace.Embodiment 11～19th, by pincers sections title complex and aluminum alkyls, form catalyzer, the Application Example for Butadiene along Isosorbide-5-Nitrae-selective polymerisation.Solvent toluene in embodiment 11～19 also can replace with chlorobenzene.
Embodiment 1 preparation pincers sections title complex (iron complex 1)
Under-78 ℃～-40 ℃ conditions, the hexane solution (1.2mL, 1.88mmol) of butyllithium is slowly added drop-wise to 2,6-bis-(N-phenyl) imido grpup bromobenzene (0.6690g, in 30mL tetrahydrofuran solution 1.84mmol), low-temp reaction adds FeCl wherein after 30 minutes
2(0.2332g, 1.88mmol), naturally rise to room temperature and continue reaction 12 hours, stopped reaction is concentrated into 5ml left and right by reaction solution, add 15ml left and right hexane, elimination insolubles, filtrate is concentrated is placed in refrigerator freeze overnight at-30 ℃, obtain 0.6200 gram of purple crystal shape compound, productive rate 60%.Its molecular formula of ultimate analysis is C
28h
31cl
2feLiN
2o2 (%): C, 59.92; H, 5.57; Cl, 12.63; N, 5.86; Fe, 9.95; Li, 1.24; N, 4.99; O, 5.70.
Embodiment 2 preparation pincers sections title complexs (iron complex 2)
Under-78 ℃～-40 ℃ conditions, by the hexane solution (1.2mL of butyllithium, 1.88mmol) be slowly added drop-wise to 2,6-bis-(N-2,6-3,5-dimethylphenyl) imido grpup bromobenzene (0.7716, in 30mL tetrahydrofuran solution 1.84mmol), low-temp reaction adds FeCl wherein after 30 minutes
2(0.2332g, 1.84mmol), naturally rise to room temperature and continue reaction 12 hours, stopped reaction is concentrated into 5ml left and right by reaction solution, add 15ml left and right hexane, elimination insolubles, filtrate is concentrated is placed in refrigerator freeze overnight at-30 ℃, obtain 0.7724 gram of purple crystal shape compound, productive rate 68%.Its molecular formula of ultimate analysis is C
32h
39cl
2feLiN
2o
2(%): C, 62.26; H, 6.37; Cl, 11.49; Fe, 9.05; Li, 1.12; N, 4.54; O, 5.18.
Embodiment 3 preparation pincers sections title complexs (iron complex 3)
Under-78 ℃～-40 ℃ conditions, by the hexane solution (1.2mL of butyllithium, 1.88mmol) be slowly added drop-wise to 2,6-bis-(N-2,6-diethyl phenyl) imido grpup bromobenzene (0.8748, in 30mL tetrahydrofuran solution 1.84mmol), low-temp reaction adds FeCl wherein after 30 minutes
2(0.2332g, 1.84mmol), naturally rise to room temperature and continue reaction 12 hours, stopped reaction is concentrated into 5ml left and right by reaction solution, add 15ml left and right hexane, elimination insolubles, filtrate is concentrated is placed in refrigerator freeze overnight at-30 ℃, obtain 0.8922 gram of purple crystal shape compound, productive rate 72%.Its molecular formula of ultimate analysis is C
36h
47cl
2feLiN
2o
2(%): C, 64.20; H, 7.03; Cl, 10.53; Fe, 8.29; Li, 1.03; N, 4.16; O, 4.75.
Embodiment 4 preparation pincers sections title complexs (iron complex 4)
Under-78 ℃～-40 ℃ conditions, by the hexane solution (1.2mL of butyllithium, 1.88mmol) be slowly added drop-wise to 2,6-bis-(N-2,6-di-tert-butyl-phenyl) imido grpup bromobenzene (1.081, in 30mL tetrahydrofuran solution 1.84mmol), low-temp reaction adds FeCl wherein after 30 minutes
2(0.2332g, 1.84mmol), naturally rise to room temperature and continue reaction 12 hours, stopped reaction is concentrated into 5ml left and right by reaction solution, add 15ml left and right hexane, elimination insolubles, filtrate is concentrated is placed in refrigerator freeze overnight at-30 ℃, obtain 0.9108 gram of purple crystal shape compound, productive rate 63%.Its molecular formula of ultimate analysis is C
44h
63cl
2feLiN
2o
2(%): C, 67.26; H, 8.08; Cl, 9.02; Fe, 7.11; Li, 0.88; N, 3.57; O, 4.07.
Embodiment 5 preparation pincers sections title complexs (iron complex 5)
Under-78 ℃～-40 ℃ conditions, by the hexane solution (1.2mL of butyllithium, 1.88mmol) be slowly added drop-wise to 2,6-bis-(N-2,6-diisopropyl phenyl) imido grpup bromobenzene (0.9780, in 30mL tetrahydrofuran solution 1.84mmol), low-temp reaction adds FeCl wherein after 30 minutes
2(0.2332g, 1.84mmol), naturally rise to room temperature and continue reaction 12 hours, stopped reaction is concentrated into 5ml left and right by reaction solution, add 15ml left and right hexane, elimination insolubles, filtrate is concentrated is placed in refrigerator freeze overnight at-30 ℃, obtain 0.9397 gram of purple crystal shape compound, productive rate 70%.Its molecular formula of ultimate analysis is C
40h
55cl
2feLiN
2o
2(%): C, 65.85; H, 7.60; Cl, 9.72; Fe, 7.65; Li, 0.95; N, 3.84; O, 4.39.
Embodiment 6 preparation pincers sections title complexs (iron complex 6)
Under-78 ℃～-40 ℃ conditions, by the hexane solution (1.2mL of butyllithium, 1.88mmol) be slowly added drop-wise to 2,6-bis-(N-2,4,6-, trimethylphenyl) imido grpup bromobenzene (0.8232, in 30mL tetrahydrofuran solution 1.84mmol), low-temp reaction adds FeCl wherein after 30 minutes
2(0.2332g, 1.84mmol), naturally rise to room temperature and continue reaction 12 hours, stopped reaction is concentrated into 5ml left and right by reaction solution, add 15ml left and right hexane, elimination insolubles, filtrate is concentrated is placed in refrigerator freeze overnight at-30 ℃, obtain 0.7720 gram of purple crystal shape compound, productive rate 65%.Its molecular formula of ultimate analysis is C
34h
43cl
2feLiN
2o
2(%): C, 63.27; H, 6.72; Cl, 10.99; Fe, 8.65; Li, 1.08; N, 4.34; O, 4.96.
Embodiment 7 preparation pincers sections title complexs (iron complex 7)
Under-78 ℃～-40 ℃ conditions, by the hexane solution (1.2mL of butyllithium, 1.88mmol) be slowly added drop-wise to 2,6-bis-(N-4-methyl-2,6-diethyl phenyl) imido grpup bromobenzene (0.9265g, in 30mL tetrahydrofuran solution 1.84mmol), low-temp reaction adds FeCl wherein after 30 minutes
2(0.2332g, 1.84mmol), naturally rise to room temperature and continue reaction 12 hours, stopped reaction is concentrated into 5ml left and right by reaction solution, add 15ml left and right hexane, elimination insolubles, filtrate is concentrated is placed in refrigerator freeze overnight at-30 ℃, obtain 0.7616 gram of purple crystal shape compound, productive rate 59%.Its molecular formula of ultimate analysis is C
38h
51cl
2feLiN
2o
2(%): C, 65.06; H, 7.33; Cl, 10.11; Fe, 7.96; Li, 0.99; N, 3.99; O, 4.56.
Embodiment 8 preparation pincers sections title complexs (iron complex 8)
Under-78 ℃～-40 ℃ conditions, by the hexane solution (1.2mL of butyllithium, 1.88mmol) be slowly added drop-wise to 2,6-bis-(N-4-methyl-2,6-di-t-butyl base phenyl) imido grpup bromobenzene (1.0297g, in 30mL tetrahydrofuran solution 1.84mmol), low-temp reaction adds FeCl wherein after 30 minutes
2(0.2332g, 1.84mmol), naturally after rising to room temperature, continue reaction 12 hours, stopped reaction is concentrated into 5ml left and right by reaction solution, add 15ml left and right hexane, elimination insolubles, filtrate is concentrated is placed in refrigerator freeze overnight at-30 ℃, obtain 0.7249 gram of purple crystal shape compound, productive rate 52%.Its molecular formula of ultimate analysis is C
42h
59cl
2feLiN
2o
2(%): C, 66.58; H, 7.85; Cl, 9.36; Fe, 7.37; Li, 0.92; N, 3.70; O, 4.22.
Embodiment 9 preparation pincers sections title complexs (iron complex 9)
Under-78 ℃～-40 ℃ conditions, by the hexane solution (1.2mL of butyllithium, 1.88mmol) be slowly added drop-wise to 2,6-bis-((2,6-dimethoxy-4 '-aminomethyl phenyl) acetylimino)-4-methyl bromobenzene (1.0184, in 30mL tetrahydrofuran solution 1.84mmol), low-temp reaction adds FeCl wherein after 30 minutes
2(0.2332g, 1.84mmol), naturally rises to room temperature and continues reaction 12 hours, stopped reaction is concentrated into 5ml left and right by reaction solution, adds 15ml left and right hexane, elimination insolubles, filtrate is concentrated is placed in refrigerator freeze overnight at-30 ℃, obtains 0.7587 gram of target compound, productive rate 57%.Its molecular formula of ultimate analysis is C
35h
45cl
2feLiN
2o
6(%): C, 58.11; H, 6.27; Cl, 9.80; Fe, 7.72; Li, 0.96; N, 3.87; O, 13.27.
Embodiment 10 preparation pincers sections title complexs (iron complex 10)
Under-78 ℃～-40 ℃ conditions, by the hexane solution (1.2mL of butyllithium, 1.88mmol) be slowly added drop-wise to 2,6-bis-[(2, the chloro-4-methyl of 6-bis-) benzoylimino base]-4-methyl bromobenzene (1.2794, in 30mL tetrahydrofuran solution 1.84mmol), low-temp reaction adds FeCl wherein after 30 minutes
2(0.2332g, 1.84mmol), naturally rises to room temperature and continues reaction 12 hours, stopped reaction is concentrated into 5ml left and right by reaction solution, adds 15ml left and right hexane, elimination insolubles, filtrate is concentrated is placed in refrigerator freeze overnight at-30 ℃, obtains 0.9936 gram of target compound, productive rate 54%.Its molecular formula of ultimate analysis is C
43h
41cl
6feLiN
2o
2(%): C, 57.81; H, 4.63; Cl, 23.81; Fe, 6.25; Li, 0.78; N, 3.14; O, 3.58.
Embodiment 11
In glove box, measure 9ml toluene and be placed in 25ml reaction flask, add the AlMe that is dissolved in 20 μ mol iron complex 2,500 μ mol in 1ml toluene
3, the solution stirring of gained adds the divinylic monomer of 500 times of iron complexes 2 by mol after 5 minutes.React on 20 ℃ and carry out 30 minutes, after the ethanolic soln that adds 1mL to contain 10% hydrochloric acid (volume ratio) of 1%BHT stops, pour sedimentation in ethanol into, obtain white solid product.This product is placed in to vacuum drying oven, at 40 ℃, is dried 48 hours.Obtain polyhutadiene, net weight 0.385g, transformation efficiency 71.1%.With the molecular weight of gpc analysis polyhutadiene, M
n=86.0 ten thousand, M
w/ M
n=5.03.Along Isosorbide-5-Nitrae content 70.6%.
Embodiment 12
In glove box, measure 9ml toluene and be placed in 25ml reaction flask, add the AlMe that is dissolved in 20 μ mol iron complex 3,500 μ mol in 1ml toluene
3, the solution stirring of gained adds the divinylic monomer of 500 times of iron complexes 3 by mol after 5 minutes.React on 20 ℃ and carry out 30 minutes, after the ethanolic soln that adds 1mL to contain 10% hydrochloric acid (volume ratio) of 1%BHT stops, pour sedimentation in ethanol into, obtain white solid product.This product is placed in to vacuum drying oven, at 40 ℃, is dried 48 hours.Obtain polyhutadiene, net weight 0.426g, transformation efficiency 78.9%.With the molecular weight of the poly-polyhutadiene of gpc analysis, M
n=116.0 ten thousand, M
w/ M
n=7.15.Along Isosorbide-5-Nitrae content 73.2%.
Embodiment 13
In glove box, measure 9ml toluene and be placed in 25ml reaction flask, add the AlMe that is dissolved in 20 μ mol iron complex 5,500 μ mol in 1ml toluene
3, the solution stirring of gained adds the divinylic monomer of 500 times of iron complexes 5 by mol after 5 minutes.React on 20 ℃ and carry out 30 minutes, after the ethanolic soln that adds 1mL to contain 10% hydrochloric acid (volume ratio) of 1%BHT stops, pour sedimentation in ethanol into, obtain white solid product.This product is placed in to vacuum drying oven, at 40 ℃, is dried 48 hours.Obtain polyhutadiene, net weight 0.426g, transformation efficiency 78.9%.With the molecular weight of the poly-polyhutadiene of gpc analysis, M
n=5.54 ten thousand, M
w/ M
n=2.95.Along Isosorbide-5-Nitrae content 75.3%.
Embodiment 14
In glove box, measure 9ml toluene and be placed in 25ml reaction flask, add the AlMe that is dissolved in 20 μ mol iron complex 5,500 μ mol in 1ml toluene
3, the solution stirring of gained adds the divinylic monomer of 1000 times of iron complexes 5 by mol after 5 minutes.React on 20 ℃ and carry out 60 minutes, after the ethanolic soln that adds 1mL to contain 10% hydrochloric acid (volume ratio) of 1%BHT stops, pour sedimentation in ethanol into, obtain white solid product.This product is placed in to vacuum drying oven, at 40 ℃, is dried 48 hours.Obtain polyhutadiene, net weight 0.898g, transformation efficiency 83.2%.With the molecular weight of the poly-polyhutadiene of gpc analysis, M
n=16.5 ten thousand, M
w/ M
n=2.91.Along Isosorbide-5-Nitrae content 71.4%.
Embodiment 15
In glove box, measure 9ml toluene and be placed in 25ml reaction flask, add the AlMe that is dissolved in 20 μ mol iron iron complex 5,500 μ mol in 1ml toluene
3, the solution stirring of gained adds the divinylic monomer of 2000 times of iron complexes 5 by mol after 5 minutes.React on 20 ℃ and carry out 60 minutes, after the ethanolic soln that adds 1mL to contain 10% hydrochloric acid (volume ratio) of 1%BHT stops, pour sedimentation in ethanol into, obtain white solid product.This product is placed in to vacuum drying oven, at 40 ℃, is dried 48 hours.Obtain polyhutadiene, net weight 1.636g, transformation efficiency 75.8%.With the molecular weight of the poly-polyhutadiene of gpc analysis, M
n=29.1 ten thousand, M
w/ M
n=2.89.Along Isosorbide-5-Nitrae content 75.5%.
Embodiment 16
In glove box, measure 9ml toluene and be placed in 25ml reaction flask, add the AlMe that is dissolved in 20 μ mol iron complex 5,500 μ mol in 1ml toluene
3, the solution stirring of gained adds the divinylic monomer of 500 times of iron complexes 5 by mol after 5 minutes.React on 0 ℃ and carry out 600 minutes, after the ethanolic soln that adds 1mL to contain 10% hydrochloric acid (volume ratio) of 1%BHT stops, pour sedimentation in ethanol into, obtain white solid product.This product is placed in to vacuum drying oven, at 40 ℃, is dried 48 hours.Obtain polyhutadiene, net weight 0.340g, transformation efficiency 62.9%.With the molecular weight of the poly-polyhutadiene of gpc analysis, M
n=2.72 ten thousand, M
w/ M
n=1.99.Along Isosorbide-5-Nitrae content 72.6%.
Embodiment 17
In glove box, measure 9ml toluene and be placed in 25ml reaction flask, add the AlMe that is dissolved in 20 μ mol iron complex 5,500 μ mol in 1ml toluene
3, the solution stirring of gained adds the divinylic monomer of 500 times of iron complexes 5 by mol after 5 minutes.React on-20 ℃ and carry out 1080 minutes, after the ethanolic soln that adds 1mL to contain 10% hydrochloric acid (volume ratio) of 1%BHT stops, pour sedimentation in ethanol into, obtain white solid product.This product is placed in to vacuum drying oven, at 40 ℃, is dried 48 hours.Obtain polyhutadiene, net weight 0.292g, transformation efficiency 54.1%.With the molecular weight of the poly-polyhutadiene of gpc analysis, M
n=1.67 ten thousand, M
w/ M
n=2.27.Along Isosorbide-5-Nitrae content 60.4%.
Embodiment 18
In glove box, measure 9ml toluene and be placed in 25ml reaction flask, add the AlEt that is dissolved in 20 μ mol iron complex 5,500 μ mol in 1ml toluene
3, the solution stirring of gained adds the divinylic monomer of 500 times of iron complexes 5 by mol after 5 minutes.React on 20 ℃ and carry out 35 minutes, after the ethanolic soln that adds 1mL to contain 10% hydrochloric acid (volume ratio) of 1%BHT stops, pour sedimentation in ethanol into, obtain white solid product.This product is placed in to vacuum drying oven, at 40 ℃, is dried 48 hours.Obtain polyhutadiene, net weight 0.217g, transformation efficiency 40.2%.With the molecular weight of gpc analysis polyhutadiene, M
n=17.6 ten thousand, M
w/ M
n=2.62.Along Isosorbide-5-Nitrae content 71.0%.
Embodiment 19
In glove box, measure 9ml toluene and be placed in 25ml reaction flask, add be dissolved in 20 μ mol iron complex 5,500 μ mol in 1ml toluene Al (
ibu)
3, the solution stirring of gained adds the divinylic monomer of 500 times of iron complexes 5 by mol after 5 minutes.React on 20 ℃ and carry out 180 minutes, after the ethanolic soln that adds 1mL to contain 10% hydrochloric acid (volume ratio) of 1%BHT stops, pour sedimentation in ethanol into, obtain white solid product.This product is placed in to vacuum drying oven, at 40 ℃, is dried 48 hours.Obtain polyhutadiene, net weight 0.241g, transformation efficiency 44.6%.With the molecular weight of gpc analysis polyhutadiene, M
n=64.7 ten thousand, M
w/ M
n=5.67.Along Isosorbide-5-Nitrae content 75.0%.
Claims (8)
1. a pincers sections title complex, is based on [NCN]
-the pincers sections title complex of coordination, has following structure:
Wherein, R
1for the substituting group on skeleton phenyl ring, be hydrogen or methyl; R
2for the substituting group on imines carbon, be methyl, phenyl or hydrogen; R
3for methyl, ethyl, sec.-propyl, the tertiary butyl, hydrogen, methoxyl group or chlorine; R
4for methyl or hydrogen; X is that halogen anion is Cl
-.
2. pincers sections title complex according to claim 1, is characterized in that, is pincerlike iron complex 2,3 or 5, concrete,
Pincerlike iron complex 2:R
1=H, R
2=H, R
3=Me, R
4=H, X=Cl
-;
Pincerlike iron complex 3:R
1=H, R
2=H, R
3=Et, R
4=H, X=Cl
-;
Pincerlike iron complex 5:R
1=H, R
2=H, R
3=
ipr, R
4=H, X=Cl
-.
3. the preparation method of the pincers sections title complex of a claim 1, under-78 ℃～-40 ℃ conditions, the hexane solution of butyllithium is added in the tetrahydrofuran solution of part, the molar ratio of butyllithium and part is 1.1～1: 1, reacts and within 0.5～1 hour, obtains reaction solution, by the tetrahydrofuran (THF) adducts (FeCl of ferrous chloride or ferrous chloride
2)
2(THF)
3powder join in reaction solution, be naturally warming up to room temperature and continue again to react 4～5 hours, the molar ratio of ferrous chloride and part is 1.2～1: 1, after reaction solution is concentrated after reaction finishes, add hexane, filtration and recrystallization obtains pincerlike iron complex, described part is: 2, 6-bis-(N-phenyl) imido grpup bromobenzene, 2, 6-bis-(N-2, 6-3,5-dimethylphenyl) imido grpup bromobenzene, 2, 6-bis-(N-2, 6-diethyl phenyl) imido grpup bromobenzene, 2, 6-bis-(N-2, 6-di-tert-butyl-phenyl) imido grpup bromobenzene, 2, 6-bis-(N-2, 6-diisopropyl phenyl) imido grpup bromobenzene, 2, 6-bis-(N-2, 4, 6-, trimethylphenyl) imido grpup bromobenzene, 2, 6-bis-(N-4-methyl-2, 6-diethyl phenyl) imido grpup bromobenzene, 2, 6-bis-(N-4-methyl-2, 6-di-t-butyl base phenyl) imido grpup bromobenzene, 2, 6-bis-[(2, 6-dimethoxy-4 '-aminomethyl phenyl) acetylimino]-4-methyl bromobenzene.
4. the preparation method of pincers sections title complex according to claim 3, is characterized in that, the concentration of the hexane solution of butyllithium is 1.0～2.0mol/L.
5. a purposes for the pincers sections title complex of claim 2, by [NCN]
-the pincers sections title complex of coordination, aluminum alkyls form catalyzer, for Butadiene along Isosorbide-5-Nitrae-selective polymerisation; Described aluminum alkyls is AlMe
3, AlEt
3or Al (
ibu)
3; Aluminum alkyls with based on [NCN]
-the ratio of the pincers sections title complex of coordination is 10～50: 1.
6. the purposes of pincers sections title complex according to claim 5, is characterized in that, described aluminum alkyls is AlMe
3; Aluminum alkyls with based on [NCN]
-the ratio of the pincers sections title complex of coordination is 25: 1.
7. according to the purposes of the pincers sections title complex described in claim 5 or 6, it is characterized in that, with [NCN]
-the pincers sections title complex of coordination and aluminum alkyls form catalyzer, and Butadiene is as follows along step and the condition of Isosorbide-5-Nitrae-selective polymerisation: measure based on [NCN]
-toluene or the chlorobenzene solution of the pincers sections title complex of coordination are placed in reactor, add aluminum alkyls, stir 5 minutes; Add by mol 500～5000 times to the divinylic monomer of pincers sections title complex, polyreaction is carried out 0.25～18 hour at-40～40 ℃; Add hydrochloric acid and the ethanolic soln of the 2,6 di tert butyl 4 methyl phenol that contains by mass 1% to stop polymerization; Pouring reactant in ethanol sedimentation and go out polymkeric substance, is white solid product.
8. the purposes of pincers sections title complex according to claim 7, is characterized in that, in the hydrochloric acid and ethanolic soln of described 2,6 di tert butyl 4 methyl phenol, the volume ratio of hydrochloric acid and ethanol is 1: 8～10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210096766.5A CN102633840B (en) | 2012-04-05 | 2012-04-05 | Clamp-type iron complex and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210096766.5A CN102633840B (en) | 2012-04-05 | 2012-04-05 | Clamp-type iron complex and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102633840A CN102633840A (en) | 2012-08-15 |
| CN102633840B true CN102633840B (en) | 2014-12-10 |
Family
ID=46618432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210096766.5A Expired - Fee Related CN102633840B (en) | 2012-04-05 | 2012-04-05 | Clamp-type iron complex and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102633840B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214357A (en) * | 2013-05-01 | 2013-07-24 | 吉林大学 | Compound 2-bromo-3-bromomethyl benzaldehyde, and synthesis method and application thereof |
| CN103232365B (en) * | 2013-05-01 | 2015-04-22 | 吉林大学 | Schiff base compound, and synthesis method and application thereof |
| CN105001255B (en) * | 2015-07-23 | 2017-12-22 | 吉林大学 | [N, N, N, N] tetradentate ligandses fourth officer group 4 transition metal complexes and its production and use |
| CN109827989B (en) * | 2019-02-13 | 2021-07-09 | 首都师范大学 | Domestic blood fluorine concentration detect reagent box |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186663A (en) * | 2007-11-13 | 2008-05-28 | 中国科学院长春应用化学研究所 | Rare earth catalyst for catalyzing syn form 1,4-selectivity polymerization of isoprene or butadiene |
| CN102127116A (en) * | 2010-11-26 | 2011-07-20 | 吉林大学 | Caliper type chromium complex and preparation method and application thereof |
-
2012
- 2012-04-05 CN CN201210096766.5A patent/CN102633840B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186663A (en) * | 2007-11-13 | 2008-05-28 | 中国科学院长春应用化学研究所 | Rare earth catalyst for catalyzing syn form 1,4-selectivity polymerization of isoprene or butadiene |
| CN102127116A (en) * | 2010-11-26 | 2011-07-20 | 吉林大学 | Caliper type chromium complex and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| GiovanniRiccietal..Polymerizationof1 3-dienes with iron complexes based catalysts Influence of the ligand on catalyst activity and stereospecificity.《Journal of Molecular Catalysis A: Chemical》.2003 * |
| Polymerization of 1,3-dienes with iron complexes based catalysts Influence of the ligand on catalyst activity and stereospecificity;Giovanni Ricci et al.;《Journal of Molecular Catalysis A: Chemical》;20030915;第204-205卷;第287页摘要，第290页表2 * |
| 朱勇.铁系聚烯烃催化剂的合成及应用.《合成树脂及塑料》.2008,第25卷(第2期), * |
| 铁系聚烯烃催化剂的合成及应用;朱勇;《合成树脂及塑料》;20080923;第25卷(第2期);第7页图1，第10页左栏第1段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102633840A (en) | 2012-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Pyrrolide-supported lanthanide alkyl complexes. influence of ligands on molecular structure and catalytic activity toward isoprene polymerization | |
| Stern et al. | Manipulation of organolanthanide coordinative unsaturation. Synthesis, structures, structural dynamics, comparative reactivity, and comparative thermochemistry of dinuclear. mu.-hydrides and. mu.-alkyls with [. mu.-R2Si (Me4C5)(C5H4)] 2 supporting ligation | |
| EP1379562B1 (en) | Supported olefin polymerization catalysts | |
| Wang et al. | NNN-Tridentate Pyrrolyl Rare-Earth Metal Complexes: Structure and Catalysis on Specific Selective Living Polymerization of Isoprene | |
| Pan et al. | Bis (oxazolinyl) phenyl-ligated rare-earth-metal complexes: highly regioselective catalysts for cis-1, 4-polymerization of isoprene | |
| Gao et al. | Chromium complexes supported by phenanthrene-imine derivative ligands: synthesis, characterization and catalysis on isoprene cis-1, 4 polymerization | |
| Luo et al. | Rare earth metal bis (alkyl) complexes bearing a monodentate arylamido ancillary ligand: Synthesis, structure, and Olefin polymerization catalysis | |
| Jing et al. | Synthesis and characterization of aminopyridine iron (II) chloride catalysts for isoprene polymerization: Sterically controlled monomer enchainment | |
| CN102633840B (en) | Clamp-type iron complex and preparation method and application thereof | |
| Gong et al. | Regio-and stereo-selective polymerization of 1, 3-butadiene catalyzed by phosphorus–nitrogen PN 3-pincer cobalt (ii) complexes | |
| CN109053937B (en) | Alkyl substituted pyridylamine iron-based catalyst and preparation method and application thereof | |
| CN101157737B (en) | Aza cyclic carbine rear earth catalyst for crystallinity 3,4-polyisoprene | |
| Lu et al. | Monoalkyllanthanide Complexes with New β-Diketiminato Derivative Dianionic Ligands | |
| KR20170045736A (en) | Ligand based chromium catalyst and application in catalyzing ethylene oligomerization | |
| Lyubov et al. | N, N ‘-Diisopropyl-N ‘‘-bis (trimethylsilyl) guanidinate Ligand as a Supporting Coordination Environment in Yttrium Chemistry. Synthesis, Structure, and Properties of Complexes [(Me3Si) 2NC (N i-Pr) 2] YCl2 (THF) 2,[(Me3Si) 2NC (N i-Pr) 2] Y (CH2SiMe3) 2 (THF) 2, and [(Me3Si) 2NC (N i-Pr) 2] Y [(μ-H)(μ-Et) 2BEt] 2 (THF) | |
| Kempe | Rare earth polymerization catalysts supported by bulky aminopyridinato ligands | |
| Jia et al. | Scandium and gadolinium complexes with aryldiimine NCN pincer ligands: Synthesis, characterization, and catalysis on isoprene and 1, 5-hexadiene polymerization | |
| CN111303214B (en) | Pyridine tertiary amine iron complex, preparation method thereof and method for catalyzing polymerization of conjugated diene by using same | |
| Wang et al. | Mono (boratabenzene) rare-earth metal dialkyl complexes: synthesis, structure and catalytic behaviors for styrene polymerization | |
| US9200092B2 (en) | η5:η1-cyclopentadienylidene-phosphorane constrained geometry complexes of rare earth metals | |
| CN108484809B (en) | Olefin polymerization catalyst | |
| Hao et al. | Nickel complexes bearing N, N, N-tridentate quinolinyl anilido–imine ligands: Synthesis, characterization and catalysis on norbornene addition polymerization | |
| Ji et al. | Synthesis of Ti, Zr, and Hf complexes with a new tetra-azane ligand by one-pot HCl-elimination and their properties as catalysts for production of UHMWPE | |
| BR112014005747B1 (en) | bis-imine complex of lanthanides, catalytic system comprising said bis-imine complex, process for the (co) polymerization of conjugated dienes and polymerization process of dienes | |
| Li et al. | Zirconium complexes based on an ethylene linked amidinate–amido ligand: synthesis, characterization and ethylene polymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141210 Termination date: 20160405 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |