CN102127116A - Caliper type chromium complex and preparation method and application thereof - Google Patents
Caliper type chromium complex and preparation method and application thereof Download PDFInfo
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- CN102127116A CN102127116A CN2010105596018A CN201010559601A CN102127116A CN 102127116 A CN102127116 A CN 102127116A CN 2010105596018 A CN2010105596018 A CN 2010105596018A CN 201010559601 A CN201010559601 A CN 201010559601A CN 102127116 A CN102127116 A CN 102127116A
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- chromic compound
- chromic
- compound
- pincers type
- bromobenzene
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Abstract
The invention relates to a caliper type chromium complex and a preparation method and application thereof, and belongs to the technical field of catalysts. The caliper type chromium complex is a [NCN]-ligand-based caliper type chromium complex. The preparation method comprises the following steps of: adding hexane solution of butyl lithium into tetrahydrofuran solution of a ligand dropwise for reaction; adding a tetrahydrofuran adduct of chromium trichloride or chromium dichloride; and heating the mixture to room temperature naturally and reacting to obtain the caliper type chromium complex. The ligand can be 2,6-bis(N-2,6- phenyl)imido bromobenzene. The caliper type chromium complex, alkyl aluminum and organic boron salt serving as catalysts are used for catalyzing selective polymerization of isoprene or butadiene. The caliper type chromium complex has high stability and is convenient to prepare; the catalytic system can be used for selectively catalyzing polymerization of the isoprene or the butadiene, and has low using amount of a cocatalyst, high polymerization speed, high conversion rate and high anti-1,4 selectivity; and the caliper type chromium complex can be applied actually by replacing natural trans-1,4 rubber.
Description
Technical field
The invention belongs to the technical field of catalyzer, particularly a kind of catalyzer that comprises pincers type chromic compound, it is anti-1 to be used for catalysis isoprene or divinyl, the catalyzer of 4-selective polymerisation.
Background technology
Anti-form-1,4-polyisoprene are a kind of of polyisoprene rubber, its chemical constitution and the cis of being familiar with 1, and the 4-polyisoprene is identical, and two kinds of polymkeric substance belong to isomers, but the spatial orientation difference of group on two key units in the polymer chain.Anti-form-1, two keys have comparative advantage with transconfiguration in the 4-polyisoprene molecular chain, and cis-1, the two keys of 4-polyisoprene molecular chain are based on cis-structure.These two kinds of different arrangement modes cause the huge difference on the performance.Cis 1, the 4-polyisoprene rubber has typical rubber elastomer characteristics, and every performance classes is similar to natural gum, and is slow as crystallization at room temperature, and the good mechanical performance is arranged.And anti-form-1,4 polyisoprene rubbers at room temperature exist with crystal form, have high rigidity, in case and outside temperature rises to 60 ℃, the crystallization fusion demonstrates thermoplasticity.
Similar to natural rubber, natural anti-form-1,4 rubber derive from the milk of certain plants, comprise gutta-percha tree and taraxacum herbaceous plant.Common is Gu Tapu rubber, have comparative advantage in its composition (99%) be to be present in trans 1 in the bark of eucommia myron, the 4-isoprene is so also claim Chinese gutta percha.The yield rate of Gu Tapu rubber is low, use less, consider to be unwell to establishing in large scale from economic angle, so it is limited to get the scale of Gu Tapu glue from natural phant refining for a long time, but pass through in recent years synthetic anti-form-1, the research of 4 polyisoprene, find that it can and use with all-purpose gum kinds such as NR, SBR, BR, not only can be quantitatively as the surrogate of traditional common glue, can also on some performance, learn from other's strong points to offset one's weaknesses with them, bring into play the effect of its uniqueness, caused the concern of rubber industry circle.As when and when being used for tyre surface, the sidewall of tire, can improve wear-resistingly, reduce rolling resistance, thereby reduce oil consumption.Therefore develop transly 1, the 4-polyisoprene rubber has important commercial value.
On the other hand, high trans-polybutadiene has resistance to fatigue, wear resistance, resistance to tearing and the low-temperature performance of lower compression heat generation, excellence, and its tackiness and green strength are also very outstanding, in tire industry, can be used as and join glue, in order to improve the performance of tire, be the desirable sizing material of development high-performance radial.Therefore it is anti-1 to develop highly selective, and 4-divinyl and isoprene polymerization catalyzer are very necessary.
Can in the presence of catalyzer, aggregate into isoprene monomer anti-1,4-polyisoprene, along 1,4-polyisoprene and 3,4-polyisoprene; Can in the presence of catalyzer, aggregate into anti-1, suitable 1 and 1,2-polyhutadiene with divinylic monomer.But it is different using the ratio of the various polymkeric substance that different catalyzer obtains, and it is very difficult selectively controlling each polymer ratio in the actually operating.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of based on [NCN]
-Coordinate pincers type chromic compound; Provide catalysis isoprene or divinyl anti-1, the catalyzer of 4-selective polymerisation, this catalyzer are by based on [NCN]
-Coordinate pincers type chromic compound, aluminum alkyls and organic boron salt are formed; Provide this catalyzer anti-1, the concrete application in the 4-selective polymerisation at catalysis isoprene or divinyl.
For realizing purpose of the present invention, provide concrete technical scheme as follows.
A kind of pincers type chromic compound is based on [NCN]
-Coordinate pincers type chromic compound 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.; R
2Being the substituting group on the imines carbon, can be methyl, ethyl, sec.-propyl, the tertiary butyl, phenyl or hydrogen etc.; R
3Be methyl, ethyl, sec.-propyl, the tertiary butyl, hydrogen, methoxyl group, fluorine, chlorine, bromine or iodine etc.; R
4Be methyl, ethyl, sec.-propyl, the tertiary butyl or hydrogen etc.; *=1～2.
By above-mentioned based on [NCN]
-Coordinate pincers type chromic compound preferably has chromic compound 1～chromic compound 10, and concrete is,
Chromic compound 1:R
1=H, R
2=H, R
3=H, R
4=H, x=2;
Chromic compound 2:R
1=H, R
2=H, R
3=Me, R
4=H, x=2;
Chromic compound 3:R
1=H, R
2=H, R
3=Et, R
4=H, x=2;
Chromic compound 4:R
1=H, R
2=H, R
3=
tBu, R
4=H, x=2;
Chromic compound 5:R
1=H, R
2=H, R
3=
iPr, R
4=H, x=2;
Chromic compound 6:R
1=H, R
2=H, R
3=Me, R
4=H, x=1;
Chromic compound 7:R
1=H, R
2=H, R
3=Et, R
4=H, x=1;
Chromic compound 8:R
1=H, R
2=H, R
3=
iPr, R
4=H, x=1;
Chromic compound 9:R
1=Me, R
2=Me, R
3=OCH
3, R
4=Me, x=2;
Chromic compound 10:R
1=Br, R
2=Ph, R
3=Cl, R
4=Br, x=2.
R more preferably
1Be hydrogen, R
2Be hydrogen, R
3Be ethyl, R
4Be hydrogen.
A kind of preparation method who clamps the type chromic compound, its reaction scheme is as follows:
Concrete preparation process and condition are, under-40 ℃～-78 ℃ 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 be mixed with reaction solution in 0.5～1 hour under-40 ℃～-78 ℃ temperature; The tetrahydrofuran (THF) adducts of chromium trichloride or chromium dichloride is joined in the reaction solution, be warming up to room temperature naturally and continued to react 4～5 hours again, the molar ratio of chromium trichloride or chromium dichloride and part is 1.2～1: 1; Vacuum is taken out and is desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains pincers type chromic compound; Described part is 2,6-two (N-2, the 6-phenyl) imido grpup bromobenzene, 2,6-two (N-2,6-3,5-dimethylphenyl) imido grpup bromobenzene, 2,6-two (N-2,6-diethyl phenyl) imido grpup bromobenzene, 2,6-two (N-2, the 6-di-tert-butyl-phenyl) imido grpup bromobenzene, 2,6-two (N-2,6-diisopropyl phenyl) imido grpup bromobenzene, 2,6-two [(2,6-dimethoxy, 4-aminomethyl phenyl) acetylimino] 4-methyl bromobenzene or 2,6-two [(2,6-dichloro, 4-bromo) benzoylimino base] 4-bromine bromobenzene.
The concentration of the hexane solution of butyllithium is 1.0～2.0mol/L preferably; The concentration of the tetrahydrofuran solution of part is to the not influence of preparation chromic compound.
The catalyzer of catalysis isoprene of the present invention or divinyl selective polymerisation, composition has based on [NCN]
-Coordinate pincers type chromic compound, aluminum alkyls and organic boron salt, routine in molar ratio pincers type chromic compound: aluminum alkyls: organic boron salt=1: 10～40: 1.
Described aluminum alkyls is: AlMe
3, AlEt
3, Al (
iBu)
3Or AlEt
2Cl, preferred Al (
iBu)
3
Described organic boron salt is [Ph
3C] [B (C
6F
5)
4], [PhNMe2H] [B (C
6F
5)
4] or B (C
6F
5) 3, preferred [Ph
3C] [B (C
6F
5)
4].
The molar ratio of pincers type chromic compound and aluminum alkyls is preferably 1: 20.
The step and the condition of catalysis isoprene or divinyl selective polymerisation are as follows:
Measure based on [NCN]
-The toluene or the chlorobenzene solution of coordinate pincers type chromic compound place reactor, add aluminum alkyls and organic boron salt, stir 5 minutes; Adding is by the isoprene or the divinylic monomer of 1000 times of pincers types of mole chromic compound, and polyreaction was carried out under-20～40 ℃ 0.25～2 hour; Add hydrochloric acid and the ethanolic soln contain 1% 2,6 di tert butyl 4 methyl phenol (BHT) by mass and stop polymerization; Reactant poured into sedimentation goes out polymkeric substance in the ethanol, be white solid product.The main component of product is for poly-anti-1,4-isoprene or poly-anti-1,4-divinyl.
The toluene of pincers type chromic compound or the concentration of chlorobenzene solution can for 1 the milli rub/liter.Stop in the hydrochloric acid and ethanolic soln of polymeric BHT, hydrochloric acid and alcoholic acid volume ratio can be 1: 8～10.
White solid product is placed vacuum drying oven, and drying is 48 hours under 40 ℃.The molecular weight of polyisoprene and polyhutadiene is measured with gel permeation chromatograph, and anti-1,4 content of polyisoprene calculates with NMR (Nuclear Magnetic Resonance) spectrum.
Pincers type chromic compound good stability of the present invention, easy to prepare.These chromic compounds are alternative catalysis isoprene and polymerizing butadiene in the presence of aluminum alkyls and organic boron salt, and the promotor consumption is low, and polymerization rate is fast, the transformation efficiency height, and polymericular weight is controlled, narrow molecular weight distribution, anti-1,4 selectivity height.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
Embodiment 1 preparation pincers type chromic compounds (chromic compound 1)
Under-78 ℃ of conditions, with the hexane solution of butyllithium (1.2mL 1.88mmol) slowly is added drop-wise to 2,6-two (N-2,6-phenyl) imido grpup bromobenzene (0.6690g, in 30mL tetrahydrofuran solution 1.84mmol), low-temp reaction after 30 minutes to wherein adding CrCl
3(THF)
3(0.7043g 1.88mmol), rises to room temperature naturally and continues reaction 4 hours, solvent removed in vacuo, and resistates extracts with toluene, concentrates toluene solution, obtains bright green crystallisate title complex 1 totally 0.52 gram, productive rate 60%.Its molecular formula of ultimate analysis is C
24H
23Cl
2CrN
2O (%): C, 60.26; H, 4.85; N5.86.
Embodiment 2 preparation pincers type chromic compounds (chromic compound 2)
Under-78 ℃ of conditions, (0.86mL 1.35mmol) 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 (0.5625g, in 30mL tetrahydrofuran solution 1.34mmol), low-temp reaction after 30 minutes to wherein adding CrCl
3(THF)
3(0.5148g 1.37mmol), rises to room temperature naturally and continues reaction 4 hours, solvent removed in vacuo, and resistates extracts with toluene, concentrates toluene solution, obtains bright green crystallisate title complex 2 totally 0.50 gram, productive rate 71%.Its molecular formula of ultimate analysis is C
28H
31Cl
2CrN
2O (%): C, 62.92; H, 5.85; N, 5.24.
Embodiment 3 preparation pincers type chromic compounds (chromic compound 3)
Under-40 ℃ of conditions, (1.33mL 1.33mmol) slowly is added drop-wise to 2 with the hexane solution of butyllithium, 6-two (N-2,6-diethyl phenyl) the imido grpup bromobenzene (0.5773g, in 30mL tetrahydrofuran solution 1.21mmol), low-temp reaction after 30 minutes to wherein adding CrCl
3(THF)
3(0.5100g 1.36mmol), rises to room temperature naturally and continues reaction 4 hours, solvent removed in vacuo, and resistates extracts with toluene, concentrates toluene solution, obtains bright green crystallisate title complex 3 totally 0.42 gram, productive rate 56%.Its molecular formula of ultimate analysis is C
32H
39Cl
2CrN
2O (%): C, 65.08; H, 6.66; N, 4.74.
Embodiment 4 preparation pincers type chromic compounds (chromic compound 4)
Under-78 ℃ of conditions, (0.94mL 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 (1.0326g, in 30mL tetrahydrofuran solution 1.80mmol), low-temp reaction after 1 hour to wherein adding CrCl
3(THF)
3(0.7043g 1.88mmol), rises to room temperature naturally and continues reaction 4 hours, solvent removed in vacuo, and resistates extracts with toluene, concentrates toluene solution, obtains bright green crystallisate title complex 4 totally 0.68 gram, productive rate 55%.Its molecular formula of ultimate analysis is C
39H
53Cl
2CrN
2O (%): C, 68.01; H, 7.76; N4.07.
Embodiment 5 preparation pincers type chromic compounds (chromic compound 5)
Under-78 ℃ of conditions, (0.72mL 1.12mmol) 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 (0.5520g, in 30mL tetrahydrofuran solution 1.12mmol), low-temp reaction after 1 hour to wherein adding CrCl
3(THF)
3(0.4622g 1.12mmol), rises to room temperature naturally and continues reaction 4 hours, solvent removed in vacuo, and resistates extracts with toluene, concentrates toluene solution, obtains bright green crystallisate title complex 5 totally 0.44 gram, productive rate 62%.Its molecular formula of ultimate analysis is C
36H
47Cl
2CrN
2O (%): C, 66.86; H, 7.33; N, 4.33.
Embodiment 6 preparation pincers type chromic compounds (chromic compound 6)
Under-78 ℃ of conditions, (0.66mL 1.05mmol) 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 (0.42g, in 30mL tetrahydrofuran solution 1.00mmol), low-temp reaction after 30 minutes to wherein adding CrCl
2(THF)
2(0.27g 1.00mmol), rises to room temperature naturally and continues reaction 5 hours, solvent removed in vacuo, and resistates extracts with toluene, concentrates toluene solution, obtains purple crystal thing title complex 6 totally 0.18 gram, productive rate 55%.Its molecular formula of ultimate analysis is C
28H
31ClCrN
2O (%): C, 67.39; H, 6.26; N, 5.61.
Embodiment 7 preparation pincers type chromic compounds (chromic compound 7)
Under-78 ℃ of conditions, (0.66mL 1.05mmol) slowly is added drop-wise to 2 with the hexane solution of butyllithium, 6-two (N-2,6-diethyl phenyl) the imido grpup bromobenzene (0.48g, in 30mL tetrahydrofuran solution 1.00mmol), low-temp reaction after 30 minutes to wherein adding CrCl
2(THF)
2(0.27g 1.20mmol), rises to room temperature naturally and continues reaction 4 hours, solvent removed in vacuo, and resistates extracts with toluene, concentrates toluene solution, obtains purple crystal thing title complex 7 totally 0.22 gram, productive rate 59%.Its molecular formula of ultimate analysis is C
32H
39ClCrN
2O (%): C, 69.24; H, 7.08; N, 5.04.
Embodiment 8 preparation pincers type chromic compounds (chromic compound 8)
Under-78 ℃ of conditions, (0.66mL 1.05mmol) slowly is added drop-wise to 2 with the hexane solution of butyllithium, 6-two (N-2,6-diethyl phenyl) the imido grpup bromobenzene (0.53g, in 30mL tetrahydrofuran solution 1.00mmol), low-temp reaction after 30 minutes to wherein adding CrCl
3(THF)
3(0.27g 1.00mmol), rises to room temperature naturally and continues reaction 5 hours, solvent removed in vacuo, and resistates extracts with toluene, concentrates toluene solution, obtains purple crystal thing title complex 8 totally 0.46 gram, productive rate 64%.Its molecular formula of ultimate analysis is C
36H
47ClCrN
2O (%): C, 70.74; H, 7.75; N, 4.58.
Embodiment 9 preparation pincers type chromic compounds (chromic compound 9)
Under-78 ℃ of conditions, hexane solution (0.72mL with butyllithium, 1.12mmol) slowly be added drop-wise to 2,6-two ((2, the 6-dimethoxy, the 4-aminomethyl phenyl) acetylimino) 4-methyl bromobenzene (0.6199g, in 30mL tetrahydrofuran solution 1.12mmol), low-temp reaction after 30 minutes to wherein adding CrCl
3(THF)
3(0.4622g 1.12mmol), rises to room temperature naturally and continues reaction 4 hours, solvent removed in vacuo, and resistates extracts with toluene, concentrates toluene solution, obtains bright green crystallisate title complex 9 totally 0.37 gram, productive rate 51%.Its molecular formula of ultimate analysis is C
34H
44Cl
2CrN
2O
5(%): C, 63.00; H, 6.84; N, 4.33.
Embodiment 10 preparation pincers type chromic compounds (chromic compound 10)
Under-60 ℃ of conditions, (0.72mL 1.12mmol) slowly is added drop-wise to 2 with the hexane solution of butyllithium, 6-two [(2,6-dichloro, 4-bromo) benzoylimino base] 4-bromine bromobenzene (0.g967g, 1.12mmol) the 30mL tetrahydrofuran solution in, low-temp reaction after 30 minutes to wherein adding CrCl
3(THF)
3(0.4622g 1.12mmol), rises to room temperature naturally and continues reaction 4 hours, solvent removed in vacuo, and resistates extracts with toluene, concentrates toluene solution, obtains bright green crystallisate title complex 10 totally 0.43 gram, productive rate 50%.Its molecular formula of ultimate analysis is C
38H
30Br
3Cl
4CrN
2O (%): C, 47.34; H, 3.14; N, 2.91.
Embodiment 11 polyreactions (polyisoprene 1)
In glove box, measure the 5ml chlorobenzene and place the 25ml reaction flask, add the Al be dissolved in 10 μ mol chromic compounds, 1, the 200 μ mol in the 1ml chlorobenzene (
iBu)
3And [the Ph of 10 μ mol
3C] [B (C
6F
5)
4], the solution stirring of gained adds the isoprene monomer by 1000 times of chromic compounds 1 of mole after 5 minutes.React on 20 ℃ and carried out 2 hours, add after ethanolic soln that 1mL contains 11% 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 polyisoprene, net weight 0.11g, transformation efficiency 16.0%.With the molecular weight of gpc analysis polyisoprene, Mn=2.11 ten thousand, Mw/Mn=2.350, anti-1,4 content 81.1%.
Embodiment 12 polyreactions (polyisoprene 2)
In glove box, measure the 5ml chlorobenzene and place the 25ml reaction flask, add the Al be dissolved in 10 μ mol chromic compounds, 2, the 200 μ mol in the 1ml chlorobenzene (
iBu)
3And [the Ph of 10 μ mol
3C] [B (C
6F
5)
4], the solution stirring of gained adds the isoprene monomer by 1000 times of chromic compounds 2 of mole after 5 minutes.React on 20 ℃ and carried out 1 hour, add after ethanolic soln that 1mL contains 9% 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 polyisoprene, net weight 0.10g, transformation efficiency 14.6%.With the molecular weight of gpc analysis polyisoprene, Mn=1.15 ten thousand, Mw/Mn=1.029, anti-1,4 content 86.6%.
Embodiment 13 polyreactions (polyisoprene 3)
In glove box, measure the 5ml chlorobenzene and place the 25ml reaction flask, add the Al be dissolved in 10 μ mol chromic compounds, 3, the 200 μ mol in the 1ml chlorobenzene (
iBu)
3And [the Ph of 10 μ mol
3C] [B (C6F
5)
4], the solution stirring of gained adds the isoprene monomer by 1000 times of chromic compounds 3 of mole after 5 minutes.React on 20 ℃ and carried out 15 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 polyisoprene, net weight 0.68g, transformation efficiency 100%.With the molecular weight of gpc analysis polyisoprene, Mn=96.8 ten thousand, Mw/Mn=2.096, anti-1,4 content 84.3%.
Embodiment 14 polyreactions (polyisoprene 4)
In glove box, measure the 5ml chlorobenzene and place the 25ml reaction flask, add the Al be dissolved in 10 μ mol chromic compounds, 4, the 200 μ mol in the 1ml chlorobenzene (
iBu)
3And [the Ph of 10 μ mol
3C] [B (C
6F
5)
4], the solution stirring of gained adds the isoprene monomer by 1000 times of chromic compounds 4 of mole after 5 minutes.React on 20 ℃ and carried out 2 hours, 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 polyisoprene, net weight 0.15g, transformation efficiency 22.0%.With the molecular weight of gpc analysis polyisoprene, Mn=9.1 ten thousand, Mw/Mn=2.11, anti-1,4 content 81.1%.
Embodiment 15 polyreactions (polyisoprene 5)
In glove box, measure the 5ml chlorobenzene and place the 25ml reaction flask, add the Al be dissolved in 10 μ mol chromic compounds, 5, the 200 μ mol in the 1ml chlorobenzene (
iBu)
3And [the Ph of 10 μ mol
3C] [B (C
6F
5)
4], the solution stirring of gained adds the isoprene monomer by 1000 times of chromic compounds 5 of mole after 5 minutes.React on 20 ℃ and carried out 15 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 polyisoprene, net weight 0.65g, transformation efficiency 95.5%.With the molecular weight of gpc analysis polyisoprene, Mn=58.8 ten thousand, Mw/Mn=2.460, anti-1,4 content 83.7%.
Embodiment 16 polyreactions (polyisoprene 6)
In glove box, measure the 5ml chlorobenzene and place the 25ml reaction flask, add the Al be dissolved in 10 μ mol chromic compounds, 3, the 200 μ mol in the 1ml chlorobenzene (
iMe)
3And [the Ph of 10 μ mol
3C] [B (C
6F
5)
4], the solution stirring of gained adds the isoprene monomer by 1000 times of chromic compounds 3 of mole after 5 minutes.React on 20 ℃ and carried out 2 hours, 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 polyisoprene, net weight 0.10g, transformation efficiency 15.0%.With the molecular weight of gpc analysis polyisoprene, Mn=6.8 ten thousand, Mw/Mn=2.25, and anti-1,4 content is 83.3%.
Embodiment 17 polyreactions (polyisoprene 7)
In glove box, measure the 5ml chlorobenzene and place the 25ml reaction flask, add the Al be dissolved in 10 μ mol chromic compounds, 3, the 200 μ mol in the 1ml chlorobenzene (
iEt)
3And [the Ph of 10 μ mol
3C] [B (C
6F
5)
4], the solution stirring of gained adds the isoprene monomer by 1000 times of chromic compounds 3 of mole after 5 minutes.React on 20 ℃ and carried out 2 hours, 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 polyisoprene, net weight 0.38g, transformation efficiency 55.7%.With the molecular weight of gpc analysis polyisoprene, Mn=36.5 ten thousand, Mw/Mn=2.305, and anti-1,4 content is 80.0%.
Embodiment 18 polyreactions (polyisoprene 8)
In glove box, measure the 5ml chlorobenzene and place the 25ml reaction flask, add the Al be dissolved in 10 μ mol chromic compounds, 3, the 100 μ mol in the 1ml chlorobenzene (
iBu)
3And [the Ph of 10 μ mol
3C] [B (C
6F
5)
4], the solution stirring of gained adds the isoprene monomer by 1000 times of chromic compounds 3 of mole after 5 minutes.React on 20 ℃ and carried out 15 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 polyisoprene, net weight 0.34g, transformation efficiency 50.4%.With the molecular weight of gpc analysis polyisoprene, Mn=82.7 ten thousand, Mw/Mn=2.176, and anti-1,4 content is 79.7%.
Embodiment 19 polyreactions (polyisoprene 9)
In glove box, measure the 5ml chlorobenzene and place the 25ml reaction flask, add the Al be dissolved in 10 μ mol chromic compounds, 3, the 400 μ mol in the 1ml chlorobenzene (
iBu)
3And [the Ph of 10 μ mol
3C] [B (C
6F
5)
4], the solution stirring of gained adds the isoprene monomer by 1000 times of chromic compounds 3 of mole after 5 minutes.React on 20 ℃ and carried out 15 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 polyisoprene, net weight 0.68g, transformation efficiency 100%.With the molecular weight of gpc analysis polyisoprene, Mn=104.9 ten thousand, Mw/Mn=1.182, and anti-1,4 content is 86.2%.
Embodiment 20 polyreactions (polyisoprene 10)
In glove box, measure the 5ml chlorobenzene and place the 25ml reaction flask, add the Al be dissolved in 10 μ mol chromic compounds, 3, the 200 μ mol in the 1ml chlorobenzene (
iBu)
3And [the Ph of 10 μ mol
3C] [B (C
6F
5)
4], the solution stirring of gained adds the isoprene monomer by 1000 times of chromic compounds 3 of mole after 5 minutes.React on-20 ℃ and carried out 1 hour, 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 polyisoprene, net weight 0.03g, transformation efficiency 3.4%.With the molecular weight of gpc analysis polyisoprene, Mn=86.0 ten thousand, Mw/Mn=1.350, anti-1,4 content 84.0%.
Embodiment 21 polyreactions (polyisoprene 11)
In glove box, measure the 5ml chlorobenzene and place the 25ml reaction flask, add the Al be dissolved in 10 μ mol chromic compounds, 3, the 200 μ mol in the 1ml chlorobenzene (
iBu)
3And [the Ph of 10 μ mol
3C] [B (C
6F
5)
4], the solution stirring of gained adds the isoprene monomer by 1000 times of chromic compounds 3 of mole after 5 minutes.React on 0 ℃ and carried out 2 hours, 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 polyisoprene, net weight 0.18g, transformation efficiency 27.2%.With the molecular weight of gpc analysis polyisoprene, Mn=72.2 ten thousand, Mw/Mn=2.197, anti-1,4 content 81.7%.
Embodiment 22 polyreactions (polyisoprene 12)
In glove box, measure the 5ml chlorobenzene and place the 25ml reaction flask, add the Al (i that is dissolved in 10 μ mol chromic compounds, 3, the 200 μ mol in the 1ml chlorobenzene
BU)
3And [the Ph of 10 μ mol
3C] [B (C
6F
5)
4], the solution stirring of gained adds the isoprene monomer by 1000 times of chromic compounds 3 of mole after 5 minutes.React on 40 ℃ and carried out 15 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 polyisoprene, net weight 0.68g, transformation efficiency 100%.With the molecular weight of gpc analysis polyisoprene, Mn=68.8 ten thousand, Mw/Mn=2.134, anti-1,4 content 86.2%.
Embodiment 23 polyreactions (polyisoprene 13)
In glove box, measure 5ml toluene and place the 25ml reaction flask, add the Al be dissolved in 10 μ mol chromic compounds, 3, the 200 μ mol in the 1ml toluene (
iBu)
3And [the Ph of 10 μ mol
3C] [B (C
6F
5)
4], the solution stirring of gained adds the isoprene monomer by 1000 times of chromic compounds 3 of mole after 5 minutes.React on 20 ℃ and carried out 15 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 polyisoprene, net weight 0.64g, transformation efficiency 93.6%.With the molecular weight of gpc analysis polyisoprene, Mn=56.6 ten thousand, Mw/Mn=2.221, anti-1,4 content 80.3%.
Embodiment 24 polyreactions (polyisoprene 14)
In glove box, measure the 5ml chlorobenzene and place the 25ml reaction flask, add the Al be dissolved in 10 μ mol chromic compounds, 3, the 200 μ mol in the 1ml chlorobenzene (
iBu)
3And the B (C of 10 μ mol
6F
5)
3, the solution stirring of gained adds the isoprene monomer by 1000 times of chromic compounds 3 of mole after 5 minutes.React on 20 ℃ and carried out 15 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 polyisoprene, net weight 0.66g, transformation efficiency 96.8%.With the molecular weight of gpc analysis polyisoprene, Mn=8.67 ten thousand, Mw/Mn=2.467, anti-1,4 content 83.0%.
Embodiment 25 polyreactions (polyisoprene 16)
In glove box, measure the 5ml chlorobenzene and place the 25ml reaction flask, add the AlEt that is dissolved in 10 μ mol chromic compounds, 3, the 200 μ mol in the 1ml chlorobenzene
2[PhNMe2H] [B (C of Cl and 10 μ mol
6F
5)
4], the solution stirring of gained adds the isoprene monomer by 1000 times of chromic compounds 3 of mole after 5 minutes.React on 40 ℃ and carried out 15 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 polyisoprene, net weight 0.68g, transformation efficiency 100%.With the molecular weight of gpc analysis polyisoprene, Mn=68.8 ten thousand, Mw/Mn=2.134, anti-1,4 content 86.2%.
Embodiment 26 polyreactions (polyhutadiene 1)
In glove box, measure the 5ml chlorobenzene and place the 25ml reaction flask, add the Al be dissolved in 10 μ mol chromic compounds, 2, the 200 μ mol in the 1ml chlorobenzene (
iMe)
3And [the Ph of 10 μ mol
3C] [B (C
6F
5)
4], the solution stirring of gained adds the divinylic monomer by 1000 times of chromic compounds 2 of mole after 5 minutes.React on 20 ℃ and carried out 15 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 0.51g, transformation efficiency 94.4%.With the molecular weight of gpc analysis polyhutadiene, Mn=20.1 ten thousand, Mw/Mn=2.210, anti-1,4 content 75.5%.
Embodiment 27 polyreactions (polyhutadiene 2)
In glove box, measure the 5ml chlorobenzene and place the 25ml reaction flask, add the Al be dissolved in 10 μ mol chromic compounds, 3, the 200 μ mol in the 1ml chlorobenzene (
iEt)
3And [the Ph of 10 μ mol
3C] [B (C
6F
5)
4], the solution stirring of gained adds the divinylic monomer by 1000 times of chromic compounds 3 of mole after 5 minutes.React on 20 ℃ and carried out 15 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 0.54g, transformation efficiency 100%.With the molecular weight of the poly-polyhutadiene of gpc analysis, Mn=30.1 ten thousand, Mw/Mn=2.182, anti-1,4 content 85.0%.
Embodiment 28 polyreactions (polyhutadiene 3)
In glove box, measure the 5ml chlorobenzene and place the 25ml reaction flask, add the Al be dissolved in 10 μ mol chromic compounds, 5, the 200 μ mol in the 1ml chlorobenzene (
iBu)
3And [the Ph of 10 μ mol
3C] [B (C
6F
5)
4], the solution stirring of gained adds the divinylic monomer by 1000 times of chromic compounds 5 of mole after 5 minutes.React on 20 ℃ and carried out 15 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 0.46g, transformation efficiency 85.5%.With the molecular weight of gpc analysis polyhutadiene, Mn=23.2 ten thousand, Mw/Mn=2.315, anti-1,4 content 80.2%.
Embodiment 29 polyreactions (polyhutadiene 4)
In glove box, measure the 5ml chlorobenzene and place the 25ml reaction flask, add the Al be dissolved in 10 μ mol chromic compounds, 3, the 200 μ mol in the 1ml chlorobenzene (
iEt)
3And [the Ph of 10 μ mol
3C] [B (C
6F
5)
4], the solution stirring of gained adds the divinylic monomer by 1000 times of chromic compounds 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 0.15g, transformation efficiency 27.8%.With the molecular weight of gpc analysis polyhutadiene, Mn=20.2 ten thousand, Mw/Mn=2.425, anti-1,4 content 82.2%.
Claims (8)
1. a pincers type chromic compound is based on [NCN]
-Coordinate pincers type chromic compound has following structure:
Wherein, R
1Be hydrogen, methyl, ethyl, sec.-propyl, fluorine, chlorine, bromine, iodine, the tertiary butyl or trimethyl silicon based; R
2Be 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=1～2.
2. according to the described pincers type of claim 1 chromic compound, it is characterized in that the structure of chromic compound 1～chromic compound 10 is respectively,
Chromic compound 1:R
1=H, R
2=H, R
3=H, R
4=H, x=2;
Chromic compound 2:R
1=H, R
2=H, R
3=Me, R
4=H, x=2;
Chromic compound 3:R
1=H, R
2=H, R
3=Et, R
4=H, x=2;
Chromic compound 4:R
1=H, R
2=H, R
3=
tBu, R
4=H, x=2;
Chromic compound 5:R
1=H, R
2=H, R
3=
iPr, R
4=H, x=2;
Chromic compound 6:R
1=H, R
2=H, R
3=Me, R
4=H, x=1;
Chromic compound 7:R
1=H, R
2=H, R
3=Et, R
4=H, x=1;
Chromic compound 8:R
1=H, R
2=H, R
3=
iPr, R
4=H, x=1;
Chromic compound 9:R
1=Me, R
2=Me, R
3=OCH
3, R
4=Me, x=2;
Chromic compound 10:R
1=Br, R
2=Ph, R
3=Cl, R
4=Br, x=2.
3. according to claim 1 or 2 described pincers type chromic compounds, it is characterized in that structure is R
1Be hydrogen, R
2Be hydrogen, R
3Be ethyl, R
4Be hydrogen.
4. preparation method who clamps the type chromic compound, under-40 ℃～-78 ℃ 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 be mixed with reaction solution in 0.5～1 hour under-40 ℃～-78 ℃ temperature; The tetrahydrofuran (THF) adducts of chromium trichloride or chromium dichloride is joined in the reaction solution, be warming up to room temperature naturally and continued to react 4～5 hours again, the molar ratio of chromium trichloride or chromium dichloride and part is 1.2～1: 1; Vacuum is taken out and is desolvated, and resistates extracts with toluene, and concentrated toluene solution obtains pincers type chromic compound; Described part is 2,6-two (N-2, the 6-phenyl) imido grpup bromobenzene, 2,6-two (N-2,6-3,5-dimethylphenyl) imido grpup bromobenzene, 2,6-two (N-2,6-diethyl phenyl) imido grpup bromobenzene, 2,6-two (N-2, the 6-di-tert-butyl-phenyl) imido grpup bromobenzene, 2,6-two (N-2,6-diisopropyl phenyl) imido grpup bromobenzene, 2,6-two [(2,6-dimethoxy, 4-aminomethyl phenyl) acetylimino] 4-methyl bromobenzene or 2,6-two [(2,6-dichloro, 4-bromo) benzoylimino base] 4-bromine bromobenzene.
5. according to the preparation method of the described pincers type of claim 4 chromic compound, it is characterized in that the concentration of the hexane solution of butyllithium is 1.0～2.0mol/L.
6. the purposes of the pincers type chromic compound of a claim 1 is based on [NCN]
-Coordinate pincers type chromic compound, aluminum alkyls and organic boron salt are made catalyzer, catalysis isoprene or divinyl selective polymerisation; The composition of catalyzer example in molar ratio is a pincers type chromic compound: aluminum alkyls: organic boron salt=1: 10～40: 1; Described aluminum alkyls is AlMe
3, AlEt
3, Al (
iBu)
3Or AlEt
2Cl; Described organic boron salt is [Ph
3C] [B (C
6F
5)
4], [PhNMe2H] [B (C
6F
5)
4] or B (C
6F
5) 3.
7. according to the purposes of the described pincers type of claim 6 chromic compound, it is characterized in that the molar ratio of pincers type chromic compound, aluminum alkyls and organic boron salt is 1: 20: 1; Described aluminum alkyls be Al (
iBu)
3Described organic boron salt is [Ph
3C] [B (C
6F
5)
4].
8. according to claim 6 or 7 described pincers type chromic compounds, it is characterized in that the step and the condition of catalysis isoprene or divinyl selective polymerisation are as follows: measure based on [NCN]
-The toluene or the chlorobenzene solution of coordinate pincers type chromic compound place reactor, add aluminum alkyls and organic boron salt, stir 5 minutes; Adding is by the isoprene or the divinylic monomer of 1000 times of pincers types of mole chromic compound, and polyreaction was carried out under-20～40 ℃ 0.25～2 hour; Add contain by mass 1% 2, the hydrochloric acid of 6-di-t-butyl 4-methylphenol and ethanolic soln stop polymerization; Reactant poured into sedimentation goes out polymkeric substance in the ethanol, be white solid product.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503983A (en) * | 2011-10-13 | 2012-06-20 | 吉林大学 | Phenanthrenequinone imine ligand-based chromium complex compounds and preparation method and application thereof |
| CN102633840A (en) * | 2012-04-05 | 2012-08-15 | 吉林大学 | Clamp-type iron complex and preparation method and application thereof |
| CN108456267A (en) * | 2017-02-20 | 2018-08-28 | 中国石油化工股份有限公司 | A kind of Bis-Schiff Bases class chromic compound and its application and a kind of method preparing conjugated diene polymer |
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|---|---|---|---|---|
| CN1891721A (en) * | 2005-05-27 | 2007-01-10 | 罗门哈斯公司 | Catalytic composition and its preparation and use for preparing polymers from ethylenically unsaturated monomers |
| WO2010101993A2 (en) * | 2009-03-03 | 2010-09-10 | University Of Florida Research Foundation, Inc. | Trianionic pincer ligands, a cr(iii)/cr(v) catalytic system and its use for catalytic aerobic oxidation of organic substrates |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1891721A (en) * | 2005-05-27 | 2007-01-10 | 罗门哈斯公司 | Catalytic composition and its preparation and use for preparing polymers from ethylenically unsaturated monomers |
| WO2010101993A2 (en) * | 2009-03-03 | 2010-09-10 | University Of Florida Research Foundation, Inc. | Trianionic pincer ligands, a cr(iii)/cr(v) catalytic system and its use for catalytic aerobic oxidation of organic substrates |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503983A (en) * | 2011-10-13 | 2012-06-20 | 吉林大学 | Phenanthrenequinone imine ligand-based chromium complex compounds and preparation method and application thereof |
| CN102633840A (en) * | 2012-04-05 | 2012-08-15 | 吉林大学 | Clamp-type iron complex and preparation method and application thereof |
| CN102633840B (en) * | 2012-04-05 | 2014-12-10 | 吉林大学 | Clamp-type iron complex and preparation method and application thereof |
| CN108456267A (en) * | 2017-02-20 | 2018-08-28 | 中国石油化工股份有限公司 | A kind of Bis-Schiff Bases class chromic compound and its application and a kind of method preparing conjugated diene polymer |
| CN108456267B (en) * | 2017-02-20 | 2020-02-18 | 中国石油化工股份有限公司 | bis-Schiff base chromium complex, application thereof and method for preparing conjugated diene polymer |
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