CN102633840A - Clamp-type iron complex and preparation method and application thereof - Google Patents
Clamp-type iron complex and preparation method and application thereof Download PDFInfo
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- CN102633840A CN102633840A CN2012100967665A CN201210096766A CN102633840A CN 102633840 A CN102633840 A CN 102633840A CN 2012100967665 A CN2012100967665 A CN 2012100967665A CN 201210096766 A CN201210096766 A CN 201210096766A CN 102633840 A CN102633840 A CN 102633840A
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- 0 CCc1cccc(CC)c1*=Cc1cccc(C=*c2c(CC)cccc2CC)c1C(F)(F)F Chemical compound CCc1cccc(CC)c1*=Cc1cccc(C=*c2c(CC)cccc2CC)c1C(F)(F)F 0.000 description 5
- PNUGGYXQDMFFMR-UHFFFAOYSA-N C[O]1CCCC1 Chemical compound C[O]1CCCC1 PNUGGYXQDMFFMR-UHFFFAOYSA-N 0.000 description 2
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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]
-Coordinate pincers sections title complex, compound method and at divinyl along 1, the application in the 4-selective polymerisation.
Background technology
At present, polyolefine material has become maximum, the most a kind of polymer starting material of purposes of output in the synthetic resins.Wherein, polyhutadiene and TR 301 are important viton kinds.Polybutadiene rubber is the second largest in the world general synthesized polymer material that is only second to styrene-butadiene rubber(SBR).Advantages such as having excellent spring, strong wear resistance, resistance to low temperature, give birth to that heat is low, hysteresis loss is little, flexible resistance, resistance to cracking and dynamic property are good; Can compare favourably with tree elastomer, X 050 and paracril etc., in the production of rubber items such as doughnut, adhesive tape, emulsion tube and rubber boot, have widely and use.Polyisoprene rubber has good virgin rubber intensity, basic viscosity, ageing resistance and rebound performance, can replace tree elastomer to be applied to produce materials such as doughnut, sebific duct, sponge, sizing agent, conveying belt, medical glue.2009, the aggregate consumption of world's TR 301 was about 540,000 tons, predicted that world consumption amount in 2012 always will reach about 640,000 tons.China has become the consumption big country of polyhutadiene and polyisoprene rubber at present, but throughput has satisfied not growing consumer need, still needs import.This just require China must the faster production paces with improve technical level, wherein emphasis is researched and developed efficient catalyst exactly.
The patent of existing series discloses the catalyzer that can be used for the divinyl selective polymerisation in recent years, has all introduced the rare earth catalyst that can be used for the divinyl selective polymerisation like the patent of invention of application number 200710056309.2, the patent of invention of application number 200810050666.2; But the catalyzer that these patents are reported is not to use expensive REE, will use expensive boron additive exactly, and is difficult for preparation.
Summary of the invention
The technical problem that the present invention will solve is that [NCN] is provided
-Coordinate pincers sections title complex and preparation method thereof; And by [NCN]
-Coordinate pincers sections title complex and aluminum alkyls are made catalyzer, are used for the catalysis divinyl along 1, the 4-selective polymerisation.Pincers sections composition catalyst preparation provided by the invention is convenient, and raw material is easy to get, and does not need boron additive.
For realizing the object of the invention, provide concrete technical scheme following.
A kind of pincers sections title complex is based on [NCN]
-Coordinate pincers sections title complex has following structure:
Wherein, R
1Being the substituting group on the 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
2Be the substituting group on the 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 a halogen anion, is F
-, Cl
-, Br
-Or I
-, preferred Cl
-
By above-mentioned based on [NCN]
-Coordinate pincers sections title complex preferably has pincerlike iron complex 1～10, and concrete is:
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
1Be hydrogen, R
2Be hydrogen, R
3Be sec.-propyl, R
4Be hydrogen.
A kind of preparation method who clamps the sections title complex, its reaction scheme is following:
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 to obtain reaction solution in 0.5～1 hour; THF adducts (FeCl with ferrous chloride or ferrous chloride
2)
2(THF)
3Powder join in the reaction solution, be warming up to room temperature naturally and continued again to react 4～5 hours, the molar ratio of ferrous chloride and part is 1.2～1: 1; Add hexane after after reaction finishes reaction solution being concentrated, filtration and recrystallization promptly gets pincerlike iron complex; Described part is: 2, and 6-two (N-phenyl) imido grpup bromobenzene, 2,6-two (N-2,6-3,5-dimethylphenyl) imido grpup bromobenzene, 2; 6-two (N-2,6-diethylammonium phenyl) imido grpup bromobenzene, 2,6-two (N-2,6-di-tert-butyl-phenyl) imido grpup bromobenzene, 2; 6-two (N-2,6-diisopropyl phenyl) imido grpup bromobenzene, 2,6-two (N-2,4; 6-, trimethylphenyl) imido grpup bromobenzene, 2,6-two (N-4-methyl-2,6-diethylammonium phenyl) imido grpup bromobenzene, 2; 6-two (N-4-methyl-2,6-di-t-butyl base phenyl) imido grpup bromobenzene, 2,6-two [(2,6-dimethoxy-4 '-aminomethyl phenyl) acetylimino]-4-methyl bromobenzene, 2; 6-two [(2,6-two chloro-4-methyl) benzoylimino base]-4-methyl bromobenzene or 2,6-two [(2,6-two chloro-4-bromos) 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 does not have remarkably influenced to the preparation iron complex.
A kind of based on [NCN]
-The purposes of coordinate pincers sections title complex is by [NCN]
-Coordinate pincers sections title complex, aluminum alkyls are formed catalyzer, are used for the catalysis divinyl along 1, the 4-selective polymerisation; Said aluminum alkyls is: AlMe
3, AlEt
3, Al (
iBu)
3Or AlEt
2Cl, preferred AlMe
3Aluminum alkyls with based on [NCN]
-The ratio of coordinate pincers sections title complex is 10～50: 1, preferred 25: 1.
The catalysis divinyl is along 1, and the step and the condition of 4-selective polymerisation are following:
Measure based on [NCN]
-The toluene or the chlorobenzene solution of coordinate pincers sections title complex place reactor drum, add aluminum alkyls, stir 5 minutes; Adding is by 500～5000 times of the moles divinylic monomer to pincers sections title complex, and polyreaction was carried out 0.25～18 hour at-40～40 ℃; Adding contains 1% 2,6 di tert butyl 4 methyl phenol (BHT) by quality hydrochloric acid and ethanolic soln stop polymerization; Reactant poured into sedimentation goes out polymkeric substance in the ethanol, be white solid product.
Polymerization gained white solid product is placed vacuum drying oven, and drying is 48 hours under 40 ℃.The molecular weight of polyhutadiene is measured with gel permeation chromatograph, and the microstructure content of polyhutadiene calculates with NMR spectrum or ir spectra.
Stop in the hydrochloric acid and ethanolic soln of polymeric BHT, hydrochloric acid and alcoholic acid volume ratio 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, YLENE, chlorobenzene or mixed alkanes or BTX aromatics or mix common solvent such as halohydrocarbon but be not limited in this, preferred toluene, or chlorobenzene.Polymeric reaction temperature can change in very wide scope, and typical TR 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 convenient, can preserve under the good stability, normal temperature and not decompose in 20 days, still has catalytic activity.These pincerlike iron complexes alternative catalysis polymerizing butadiene in the presence of aluminum alkyls; 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 MWD (1.99～7.15) are all controlled, have suitable preferably-1,4 selectivity.The system that catalyzer forms is homogeneous phase, and is easy to use, and catalytic performance is stable, and temperature fluctuation range is little in the polymerization process, and reaction is control easily.
Embodiment
Following examples 1～10th, the embodiment of pincers sections complex structure and preparation, reactant wherein (raw material) discloses structure and preparing method's compound or the compound of preparing by existing method for document.Ferrous chloride among the embodiment also can be with the THF adducts (FeCl of the ferrous chloride that contains equimolar ferro element
2)
2(THF)
3Replace.Embodiment 11～19th, form catalyzer by pincers sections title complex and aluminum alkyls, are used for the catalysis divinyl along 1, the application implementation of 4-selective polymerisation example.Solvent toluene among the embodiment 11～19 also can replace with chlorobenzene.
Embodiment 1 preparation pincers sections title complex (iron complex 1)
Under-78 ℃～-40 ℃ conditions, with the hexane solution of butyllithium (1.2mL 1.88mmol) slowly is added drop-wise to 2,6-two (N-phenyl) imido grpup bromobenzene (0.6690g, in 30mL tetrahydrofuran solution 1.84mmol), low-temp reaction after 30 minutes to wherein adding FeCl
2(0.2332g 1.88mmol), rises to room temperature naturally and continues reaction 12 hours; Stopped reaction is concentrated into reaction solution about 5ml, adds 15ml left and right sides hexane, the elimination insolubles; Filtrating concentrating is placed on-30 ℃ of following freeze overnight in the refrigerator, obtains purple crystal shape compound 0.6200 gram, 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, (1.2mL 1.88mmol) slowly is added drop-wise to 2 with the hexane solution of butyllithium; 6-two (N-2; The 6-3,5-dimethylphenyl) the imido grpup bromobenzene (0.7716, in 30mL tetrahydrofuran solution 1.84mmol), low-temp reaction after 30 minutes to wherein adding FeCl
2(0.2332g 1.84mmol), rises to room temperature naturally and continues reaction 12 hours; Stopped reaction is concentrated into reaction solution about 5ml, adds 15ml left and right sides hexane, the elimination insolubles; Filtrating concentrating is placed on-30 ℃ of following freeze overnight in the refrigerator, obtains purple crystal shape compound 0.7724 gram, 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, (1.2mL 1.88mmol) slowly is added drop-wise to 2 with the hexane solution of butyllithium; 6-two (N-2; 6-diethylammonium phenyl) the imido grpup bromobenzene (0.8748, in 30mL tetrahydrofuran solution 1.84mmol), low-temp reaction after 30 minutes to wherein adding FeCl
2(0.2332g 1.84mmol), rises to room temperature naturally and continues reaction 12 hours; Stopped reaction is concentrated into reaction solution about 5ml, adds 15ml left and right sides hexane, the elimination insolubles; Filtrating concentrating is placed on-30 ℃ of following freeze overnight in the refrigerator, obtains purple crystal shape compound 0.8922 gram, 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, (1.2mL 1.88mmol) slowly is added drop-wise to 2 with the hexane solution of butyllithium; 6-two (N-2; The 6-di-tert-butyl-phenyl) the imido grpup bromobenzene (1.081, in 30mL tetrahydrofuran solution 1.84mmol), low-temp reaction after 30 minutes to wherein adding FeCl
2(0.2332g 1.84mmol), rises to room temperature naturally and continues reaction 12 hours; Stopped reaction is concentrated into reaction solution about 5ml, adds 15ml left and right sides hexane, the elimination insolubles; Filtrating concentrating is placed on-30 ℃ of following freeze overnight in the refrigerator, obtains purple crystal shape compound 0.9108 gram, 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, (1.2mL 1.88mmol) slowly is added drop-wise to 2 with the hexane solution of butyllithium; 6-two (N-2; The 6-diisopropyl phenyl) the imido grpup bromobenzene (0.9780, in 30mL tetrahydrofuran solution 1.84mmol), low-temp reaction after 30 minutes to wherein adding FeCl
2(0.2332g 1.84mmol), rises to room temperature naturally and continues reaction 12 hours; Stopped reaction is concentrated into reaction solution about 5ml, adds 15ml left and right sides hexane, the elimination insolubles; Filtrating concentrating is placed on-30 ℃ of following freeze overnight in the refrigerator, obtains purple crystal shape compound 0.9397 gram, 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, (1.2mL 1.88mmol) slowly is added drop-wise to 2 with the hexane solution of butyllithium; 6-two (N-2,4,6-; Trimethylphenyl) the imido grpup bromobenzene (0.8232, in 30mL tetrahydrofuran solution 1.84mmol), low-temp reaction after 30 minutes to wherein adding FeCl
2(0.2332g 1.84mmol), rises to room temperature naturally and continues reaction 12 hours; Stopped reaction is concentrated into reaction solution about 5ml, adds 15ml left and right sides hexane, the elimination insolubles; Filtrating concentrating is placed on-30 ℃ of following freeze overnight in the refrigerator, obtains purple crystal shape compound 0.7720 gram, 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, (1.2mL 1.88mmol) slowly is added drop-wise to 2 with the hexane solution of butyllithium; 6-two (N-4-methyl-2; 6-diethylammonium phenyl) the imido grpup bromobenzene (0.9265g, in 30mL tetrahydrofuran solution 1.84mmol), low-temp reaction after 30 minutes to wherein adding FeCl
2(0.2332g 1.84mmol), rises to room temperature naturally and continues reaction 12 hours; Stopped reaction is concentrated into reaction solution about 5ml, adds 15ml left and right sides hexane, the elimination insolubles; Filtrating concentrating is placed on-30 ℃ of following freeze overnight in the refrigerator, obtains purple crystal shape compound 0.7616 gram, 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, (1.2mL 1.88mmol) slowly is added drop-wise to 2 with the hexane solution of butyllithium; 6-two (N-4-methyl-2; 6-di-t-butyl base phenyl) the imido grpup bromobenzene (1.0297g, in 30mL tetrahydrofuran solution 1.84mmol), low-temp reaction after 30 minutes to wherein adding FeCl
2(0.2332g 1.84mmol), rises to room temperature continued reaction 12 hours naturally; Stopped reaction is concentrated into reaction solution about 5ml, adds 15ml left and right sides hexane, the elimination insolubles; Filtrating concentrating is placed on-30 ℃ of following freeze overnight in the refrigerator, obtains purple crystal shape compound 0.7249 gram, 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; Hexane solution (1.2mL with butyllithium; 1.88mmol) slowly be added drop-wise to 2,6-two ((2,6-dimethoxy-4 '-aminomethyl phenyl) acetylimino)-4-methyl bromobenzene (1.0184; 1.84mmol) the 30mL tetrahydrofuran solution in, low-temp reaction after 30 minutes to wherein adding FeCl
2(0.2332g 1.84mmol), rises to room temperature naturally and continues reaction 12 hours; Stopped reaction is concentrated into reaction solution about 5ml, adds 15ml left and right sides hexane, the elimination insolubles; Filtrating concentrating is placed on-30 ℃ of following freeze overnight in the refrigerator, gets target compound 0.7587 gram, 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, (1.2mL 1.88mmol) slowly is added drop-wise to 2 with the hexane solution of butyllithium; 6-two [(2; 6-two chloro-4-methyl) benzoylimino base]-4-methyl bromobenzene (1.2794, in 30mL tetrahydrofuran solution 1.84mmol), low-temp reaction after 30 minutes to wherein adding FeCl
2(0.2332g 1.84mmol), rises to room temperature naturally and continues reaction 12 hours; Stopped reaction is concentrated into reaction solution about 5ml, adds 15ml left and right sides hexane, the elimination insolubles; Filtrating concentrating is placed on-30 ℃ of following freeze overnight in the refrigerator, gets target compound 0.9936 gram, 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 place the 25ml reaction flask, add the AlMe that is dissolved in 20 μ mol iron complexes, 2, the 500 μ mol in the 1ml toluene
3, the solution stirring of gained adds the divinylic monomer by 500 times of iron complexes 2 of mole after 5 minutes.React on 20 ℃ and carried out 30 minutes, add after ethanolic soln that 1mL contains 10% hydrochloric acid (volume ratio) of 1%BHT stops, pour sedimentation in the ethanol into, white solid product.This product is placed vacuum drying oven, and drying is 48 hours under 40 ℃.Get 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 1,4 content 70.6%.
Embodiment 12
In glove box, measure 9ml toluene and place the 25ml reaction flask, add the AlMe that is dissolved in 20 μ mol iron complexes, 3, the 500 μ mol in the 1ml toluene
3, the solution stirring of gained adds the divinylic monomer by 500 times of iron complexes 3 of mole after 5 minutes.React on 20 ℃ and carried out 30 minutes, add after ethanolic soln that 1mL contains 10% hydrochloric acid (volume ratio) of 1%BHT stops, pour sedimentation in the ethanol into, white solid product.This product is placed vacuum drying oven, and drying is 48 hours under 40 ℃.Get polyhutadiene, net weight 0.426g, transformation efficiency 78.9%.Gather the molecular weight of polyhutadiene, M with gpc analysis
n=116.0 ten thousand, M
w/ M
n=7.15.Along 1,4 content 73.2%.
Embodiment 13
In glove box, measure 9ml toluene and place the 25ml reaction flask, add the AlMe that is dissolved in 20 μ mol iron complexes, 5, the 500 μ mol in the 1ml toluene
3, the solution stirring of gained adds the divinylic monomer by 500 times of iron complexes 5 of mole after 5 minutes.React on 20 ℃ and carried out 30 minutes, add after ethanolic soln that 1mL contains 10% hydrochloric acid (volume ratio) of 1%BHT stops, pour sedimentation in the ethanol into, white solid product.This product is placed vacuum drying oven, and drying is 48 hours under 40 ℃.Get polyhutadiene, net weight 0.426g, transformation efficiency 78.9%.Gather the molecular weight of polyhutadiene, M with gpc analysis
n=5.54 ten thousand, M
w/ M
n=2.95.Along 1,4 content 75.3%.
Embodiment 14
In glove box, measure 9ml toluene and place the 25ml reaction flask, add the AlMe that is dissolved in 20 μ mol iron complexes, 5, the 500 μ mol in the 1ml toluene
3, the solution stirring of gained adds the divinylic monomer by 1000 times of iron complexes 5 of mole after 5 minutes.React on 20 ℃ and carried out 60 minutes, add after ethanolic soln that 1mL contains 10% hydrochloric acid (volume ratio) of 1%BHT stops, pour sedimentation in the ethanol into, white solid product.This product is placed vacuum drying oven, and drying is 48 hours under 40 ℃.Get polyhutadiene, net weight 0.898g, transformation efficiency 83.2%.Gather the molecular weight of polyhutadiene, M with gpc analysis
n=16.5 ten thousand, M
w/ M
n=2.91.Along 1,4 content 71.4%.
Embodiment 15
In glove box, measure 9ml toluene and place the 25ml reaction flask, add the AlMe that is dissolved in 20 μ mol iron iron complexes, 5, the 500 μ mol in the 1ml toluene
3, the solution stirring of gained adds the divinylic monomer by 2000 times of iron complexes 5 of mole after 5 minutes.React on 20 ℃ and carried out 60 minutes, add after ethanolic soln that 1mL contains 10% hydrochloric acid (volume ratio) of 1%BHT stops, pour sedimentation in the ethanol into, white solid product.This product is placed vacuum drying oven, and drying is 48 hours under 40 ℃.Get polyhutadiene, net weight 1.636g, transformation efficiency 75.8%.Gather the molecular weight of polyhutadiene, M with gpc analysis
n=29.1 ten thousand, M
w/ M
n=2.89.Along 1,4 content 75.5%.
Embodiment 16
In glove box, measure 9ml toluene and place the 25ml reaction flask, add the AlMe that is dissolved in 20 μ mol iron complexes, 5, the 500 μ mol in the 1ml toluene
3, the solution stirring of gained adds the divinylic monomer by 500 times of iron complexes 5 of mole after 5 minutes.React on 0 ℃ and carried out 600 minutes, add after ethanolic soln that 1mL contains 10% hydrochloric acid (volume ratio) of 1%BHT stops, pour sedimentation in the ethanol into, white solid product.This product is placed vacuum drying oven, and drying is 48 hours under 40 ℃.Get polyhutadiene, net weight 0.340g, transformation efficiency 62.9%.Gather the molecular weight of polyhutadiene, M with gpc analysis
n=2.72 ten thousand, M
w/ M
n=1.99.Along 1,4 content 72.6%.
Embodiment 17
In glove box, measure 9ml toluene and place the 25ml reaction flask, add the AlMe that is dissolved in 20 μ mol iron complexes, 5, the 500 μ mol in the 1ml toluene
3, the solution stirring of gained adds the divinylic monomer by 500 times of iron complexes 5 of mole after 5 minutes.React on-20 ℃ and carried out 1080 minutes, add after ethanolic soln that 1mL contains 10% hydrochloric acid (volume ratio) of 1%BHT stops, pour sedimentation in the ethanol into, white solid product.This product is placed vacuum drying oven, and drying is 48 hours under 40 ℃.Get polyhutadiene, net weight 0.292g, transformation efficiency 54.1%.Gather the molecular weight of polyhutadiene, M with gpc analysis
n=1.67 ten thousand, M
w/ M
n=2.27.Along 1,4 content 60.4%.
Embodiment 18
In glove box, measure 9ml toluene and place the 25ml reaction flask, add the AlEt that is dissolved in 20 μ mol iron complexes, 5, the 500 μ mol in the 1ml toluene
3, the solution stirring of gained adds the divinylic monomer by 500 times of iron complexes 5 of mole after 5 minutes.React on 20 ℃ and carried out 35 minutes, add after ethanolic soln that 1mL contains 10% hydrochloric acid (volume ratio) of 1%BHT stops, pour sedimentation in the ethanol into, white solid product.This product is placed vacuum drying oven, and drying is 48 hours under 40 ℃.Get 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 1,4 content 71.0%.
Embodiment 19
In glove box, measure 9ml toluene and place the 25ml reaction flask, add the Al be dissolved in 20 μ mol iron complexes, 5, the 500 μ mol in the 1ml toluene (
iBu)
3, the solution stirring of gained adds the divinylic monomer by 500 times of iron complexes 5 of mole after 5 minutes.React on 20 ℃ and carried out 180 minutes, add after ethanolic soln that 1mL contains 10% hydrochloric acid (volume ratio) of 1%BHT stops, pour sedimentation in the ethanol into, white solid product.This product is placed vacuum drying oven, and drying is 48 hours under 40 ℃.Get 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 1,4 content 75.0%.
Claims (8)
1. a pincers sections title complex is based on [NCN]
-Coordinate pincers sections title complex has following structure:
Wherein, R
1Being the substituting group on the skeleton phenyl ring, is hydrogen, methyl, ethyl, sec.-propyl, fluorine, chlorine, bromine, iodine, the tertiary butyl or trimethyl silicon based; R
2Being the substituting group on the imines carbon, is methyl, ethyl, sec.-propyl, the tertiary butyl, phenyl or hydrogen; R
3Be methyl, ethyl, sec.-propyl, the tertiary butyl, hydrogen, methoxyl group, fluorine, chlorine, bromine or iodine; R
4Be methyl, ethyl, sec.-propyl, the tertiary butyl or hydrogen; X is a halogen anion, is F
-, Cl
-, Br
-Or I
-
2. pincers sections title complex according to claim 1 is characterized in that, is pincerlike iron complex 1～10, and concrete is,
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.
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, and the molar ratio of butyllithium and part is 1.1～1: 1, reacts to obtain reaction solution in 0.5～1 hour; THF adducts (FeCl with ferrous chloride or ferrous chloride
2)
2(THF)
3Powder join in the reaction solution, be warming up to room temperature naturally and continued again to react 4～5 hours, the molar ratio of ferrous chloride and part is 1.2～1: 1; Add hexane after after reaction finishes reaction solution being concentrated, filtration and recrystallization promptly gets pincerlike iron complex; Described part is: 2, and 6-two (N-phenyl) imido grpup bromobenzene, 2,6-two (N-2,6-3,5-dimethylphenyl) imido grpup bromobenzene, 2; 6-two (N-2,6-diethylammonium phenyl) imido grpup bromobenzene, 2,6-two (N-2,6-di-tert-butyl-phenyl) imido grpup bromobenzene, 2; 6-two (N-2,6-diisopropyl phenyl) imido grpup bromobenzene, 2,6-two (N-2,4; 6-, trimethylphenyl) imido grpup bromobenzene, 2,6-two (N-4-methyl-2,6-diethylammonium phenyl) imido grpup bromobenzene, 2; 6-two (N-4-methyl-2,6-di-t-butyl base phenyl) imido grpup bromobenzene, 2,6-two [(2,6-dimethoxy-4 '-aminomethyl phenyl) acetylimino]-4-methyl bromobenzene, 2; 6-two [(2,6-two chloro-4-methyl) benzoylimino base]-4-methyl bromobenzene or 2,6-two [(2,6-two chloro-4-bromos) benzoylimino base]-4-bromine 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. the purposes of the pincers sections title complex of a claim 1 is by [NCN]
-Coordinate pincers sections title complex, aluminum alkyls are formed catalyzer, are used for the catalysis divinyl along 1, the 4-selective polymerisation; Said aluminum alkyls is AlMe
3, AlEt
3, Al (
iBu)
3Or AlEt
2Cl; Aluminum alkyls with based on [NCN]
-The ratio of coordinate pincers sections title complex 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
3Aluminum alkyls with based on [NCN]
-The ratio of coordinate pincers sections title complex is 25: 1.
7. according to the purposes of claim 5 or 6 described pincers sections title complexs, it is characterized in that, with [NCN]
-Coordinate pincers sections title complex and aluminum alkyls are formed catalyzer, and the catalysis divinyl is along 1, and the step and the condition of 4-selective polymerisation are following: measure based on [NCN]
-The toluene or the chlorobenzene solution of coordinate pincers sections title complex place reactor drum, add aluminum alkyls, stir 5 minutes; Adding is by 500～5000 times of the moles divinylic monomer to pincers sections title complex, and polyreaction was carried out 0.25～18 hour at-40～40 ℃; Adding contains 1% 2,6 di tert butyl 4 methyl phenol by quality hydrochloric acid and ethanolic soln stop polymerization; Reactant poured into sedimentation goes out polymkeric substance in the ethanol, be 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, hydrochloric acid and alcoholic acid volume ratio are 1: 8～10.
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| CN103232365A (en) * | 2013-05-01 | 2013-08-07 | 吉林大学 | Schiff base compound, and synthesis method and application thereof |
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| CN103214357A (en) * | 2013-05-01 | 2013-07-24 | 吉林大学 | Compound 2-bromo-3-bromomethyl benzaldehyde, and synthesis method and application thereof |
| CN103232365A (en) * | 2013-05-01 | 2013-08-07 | 吉林大学 | Schiff base compound, 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 |
| CN105001255A (en) * | 2015-07-23 | 2015-10-28 | 吉林大学 | [N,N,N,N] tetradentate ligand fourth subgroup transition metal complex and preparation 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 |
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