CN102603935B - Metal bridging bis-guanyl zirconium catalyst and preparation method and application thereof - Google Patents
Metal bridging bis-guanyl zirconium catalyst and preparation method and application thereof Download PDFInfo
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- CN102603935B CN102603935B CN 201210044516 CN201210044516A CN102603935B CN 102603935 B CN102603935 B CN 102603935B CN 201210044516 CN201210044516 CN 201210044516 CN 201210044516 A CN201210044516 A CN 201210044516A CN 102603935 B CN102603935 B CN 102603935B
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Abstract
The invention provides a metal bridging bis-guanyl zirconium catalyst and a preparation method of the metal bridging bis-guanyl zirconium catalyst, in particular relates to a guanyl ligand zirconium complex catalyst taking zirconium as a central atom and having N-C-N characteristic. The preparation method comprises the following steps: using cyclohexane as a starting material under the protection of nitrogen, converting the cyclohexane to a lithium salt by utilizing butyl lithium, then adding cyanophenyl for an addition reaction, then reacting the ligand with zirconium tetrachloride, and then reacting with butyl lithium to prepare the metal bridging bis-guanyl zirconium catalyst. The synthetic method has wide applicability, the reaction condition is mild, materials are easily accessible, the price is low, the steps are simple, and the yield is high. The catalyst has good catalytic activity for a vinyl polymerization reaction.
Description
Technical field
The present invention relates to the vinyl polymerization transition-metal catalyst, in particular to a kind of two amidino groups Zr catalysts of metal bridging with N-C-N skeleton and its preparation method and application.
Background technology
At present, industrialized olefin polymerization catalysis has Ziegler-Natta type catalyzer, Phillips type catalyzer and metallocene type catalyst etc., and these catalyzer can reach the control to catalytic activity and polymer performance by the structure of regulating part.Brintzinger has reported that a class means of special bridged metallocene catalysts is not only active high, and can realize the control (H.Schnutenhaus, H.H.Brintzinger, Angew.Chem, Int.Ed., 1979,18,777.) to the polymkeric substance steric configuration.The defects such as but, all there is the synthesis condition harshness in they, and the catalyzer total recovery is low, also have in addition its catalyzer preservation condition also very harsh, easily inactivation, and synthetic method complexity, the shortcomings such as should not prepare by raw material, thereby novel non-metallocene catalyst becomes the focus of Recent study.Not long ago our study group had designed the two amidino groups parts of a class bridging, and successfully explored its syntheti c route (Sheng-Di Bai, Jian-Ping Guo, Dian-Sheng Liu, Dalton Trans., 2006, 2244.), further utilize this class part to synthesize the bridged diamidino group-IV metal compound, can access the novel Non-metallocene Catalysts System of a class, on its node configuration, similar bridging is luxuriant, but it is advantageous that the substituting group pattern conversion is various, the reaction conditions milder, be easy to preserve, there are two active centers, so two amidino groups Zr catalysts of metal bridging that this class of R and D is new and effective, there is practical value.
Summary of the invention
The purpose of this invention is to provide the two amidino groups Zr catalysts of a kind of metal bridging, this process for synthetic catalyst is simple, the reaction conditions gentleness, and raw material is easy to get, the catalytic activity had for vinyl polymerization.
The two amidino groups Zr catalysts of a kind of metal bridging provided by the invention, its structural formula is:
The preparation method of the two amidino groups Zr catalysts of a kind of metal bridging that the present invention also provides, comprise the steps:
Under the protection and ice-water bath of nitrogen, by hexahydroaniline and n-Butyl Lithium, according to 1: 1 hybrid reaction of mol ratio, solvent is tetrahydrofuran (THF), the 20-25 that its volume is the n-Butyl Lithium volume doubly, stirs, and naturally is warmed up to room temperature, keep stirring reaction 2-3 hour, obtain lithiated product solution, gained solution is placed under ice-water bath, then in above-mentioned solution, add the cyanobenzene that is equivalent to one times of mol ratio of lithiated product, stir, naturally be warmed up to room temperature, keep stirring reaction 5-6 hour, obtain adduct; Adduct is placed under ice-water bath again, add the zirconium tetrachloride that is equivalent to one times of mol ratio of previous step adduct, naturally be warmed up to room temperature, keep stirring reaction 5-6 hour, the product obtained is placed under ice-water bath again, adds the butyllithium of one times of mol ratio, naturally is warmed up to room temperature, keep stirring reaction 2-3 hour, obtain the two amidino groups Zr catalysts of metal bridging.
Compared with prior art advantage of the present invention and effect: synthetic catalyst of the present invention is raw materials used simple and easy to get, cheap, and the preparation method is simple, and productive rate is higher, has two active centers; Catalyzer has higher catalytic activity for vinyl polymerization.
The accompanying drawing explanation
The Single Crystal X-ray structure iron of the two amidino groups Zr catalysts of Fig. 1 metal bridging of the present invention
Embodiment
The specific embodiment below only provided for describing the present invention in detail, these embodiment are not for limiting the scope of the invention.
The preparation and characterization of embodiment 1 catalyzer
(1) preparation of the two amidino groups Zr catalysts of metal bridging
Under the protection and ice-water bath of nitrogen, hexahydroaniline (0.68ml, 5.88mmol) is dissolved in to tetrahydrofuran (THF) (15cm
3) in, under agitation, add at leisure the hexane solution (2.2moldm of butyllithium
-3, 2.67cm
3, 5.88mmol), the question response mixed solution continues to stir 2 hours after returning to room temperature, reaction solution is cooled to 0 ℃, add cyanophenyl (0.59cm3,5.88mmol) with syringe, the question response mixed solution continues to stir 5 hours after returning to room temperature, reaction solution is cooled to 0 ℃ again, add zirconium tetrachloride (1.43g, 5.88mmol), the question response mixed solution continues to stir 5 hours after returning to room temperature, reaction solution is cooled to 0 ℃, adds at leisure the hexane solution (2.2moldm of butyllithium
-3, 2.67cm
3, 5.88mmol), the question response mixed solution continues to stir 2 hours after returning to room temperature, reaction is drained after finishing, and the solid matter obtained dissolves with toluene, filters, add a small amount of tetrahydrofuran (THF) after filtrate is concentrated, crystallization can obtain the two amidino groups Zr catalysts of white crystal shape metal bridging.Productive rate is 92%.Part bond distance
with bond angle (°): Zr (1)-N (3) 2.242 (6), Zr (1)-N (2) 2.265 (6), Zr (1)-O (1) 2.282 (5), Zr (1)-N (1) 2.284 (6), Zr (1)-N (4) 2.297 (6), Zr (1)-Cl (2) 2.403 (2), Zr (1)-Cl (1) 2.471 (2), Zr (1)-C (14) 2.654 (8) Zr (1)-C (7) 2.694 (8), Zr (1)-Zr (2) 3.2510 (13), Zr (2)-N (2) 1.981 (6), Zr (2)-N (3) 1.987 (6), Zr (2)-O (3) 2.324 (6), Zr (2)-O (2) 2.333 (6), Zr (2)-Cl (4) 2.453 (3), Zr (2)-Cl (3) 2.482 (2), N (3)-Zr (1)-N (2) 73.8 (2), N (3)-Zr (1)-O (1) 85.9 (2), N (2)-Zr (1)-O (1) 83.6 (2), N (3)-Zr (1)-N (1) 132.6 (2), N (2)-Zr (1)-N (1) 58.9 (2), O (1)-Zr (1)-N (1) 90.0 (2), N (3)-Zr (1)-N (4) 59.3 (2), N (2)-Zr (1)-N (4) 132.8 (2), O (1)-Zr (1)-N (4) 88.3 (2), N (1)-Zr (1)-N (4) 167.8 (2), N (3)-Zr (1)-Cl (2) 93.86 (16), N (2)-Zr (1)-Cl (2) 97.03 (16), O (1)-Zr (1)-Cl (2) 179.28 (16), N (1)-Zr (1)-Cl (2) 90.68 (16), N (4)-Zr (1)-Cl (2) 90.96 (17) N (3)-Zr (1)-Cl (1) 140.84 (17), N (2)-Zr (1)-Cl (1) 140.33 (16), O (1)-Zr (1)-Cl (1) 81.62 (14), N (1)-Zr (1)-Cl (1) 84.49 (16), N (4)-Zr (1)-Cl (1) 83.31 (18), Cl (2)-Zr (1)-Cl (1) 98.16 (8) N (3)-Zr (1)-C (14) 30.3 (2), N (2)-Zr (1)-C (14) 104.0 (2), O (1)-Zr (1)-C (14) 90.8 (2), N (1)-Zr (1)-C (14) 162.7 (2), N (4)-Zr (1)-C (14) 29.5 (2), Cl (2)-Zr (1)-C (14) 88.64 (17) Cl (1)-Zr (1)-C (14) 112.8 (2), N (3)-Zr (1)-C (7) 103.6 (2), N (2)-Zr (1)-C (7) 29.87 (19), O (1)-Zr (1)-C (7) 87.7 (2), N (1)-Zr (1)-C (7) 29.06 (19), N (4)-Zr (1)-C (7) 162.6 (2) Cl (2)-Zr (1)-C (7) 93.03 (16), Cl (1)-Zr (1)-C (7) 112.76 (17), C (14)-Zr (1)-C (7) 133.7 (2), N (3)-Zr (1)-Zr (2) 36.96 (16), N (2)-Zr (1)-Zr (2) 36.90 (14), O (1)-Zr (1)-Zr (2) 85.03 (13) N (1)-Zr (1)-Zr (2) 95.70 (15), N (4)-Zr (1)-Zr (2) 96.19 (17), Cl (2)-Zr (1)-Zr (2) 95.19 (6), Cl (1)-Zr (1)-Zr (2) 166.64 (6), C (14)-Zr (1)-Zr (2) 67.13 (19), C (7)-Zr (1)-Zr (2) 66.64 (16) N (2)-Zr (2)-N (3) 86.0 (2), N (2)-Zr (2)-O (3) 96.5 (2), N (3)-Zr (2)-O (3) 176.4 (2), N (2)-Zr (2)-O (2) 176.5 (2), N (3)-Zr (2)-O (2) 97.3 (2), O (3)-Zr (2)-O (2) 80.1 (2) N (2)-Zr (2)-Cl (4) 96.82 (18), N (3)-Zr (2)-Cl (4) 99.13 (19), O (3)-Zr (2)-Cl (4) 83.09 (17), O (2)-Zr (2)-Cl (4) 83.47 (18), N (2)-Zr (2)-Cl (3) 97.09 (18), N (3)-Zr (2)-Cl (3) 94.89 (18) O (3)-Zr (2)-Cl (3) 82.33 (17), O (2)-Zr (2)-Cl (3) 81.86 (19), Cl (4)-Zr (2)-Cl (3) 160.86 (9), N (2)-Zr (2)-Zr (1) 43.37 (16), N (3)-Zr (2)-Zr (1) 42.73 (17), O (3)-Zr (2)-Zr (1) 139.87 (15) O (2)-Zr (2)-Zr (1) 140.02 (16), Cl (4)-Zr (2)-Zr (1) 98.93 (7), Cl (3)-Zr (2)-Zr (1) 100.21 (6), C (7)-N (1)-Zr (1) 93.1 (4), C (1)-N (1)-Zr (1) 141.2 (5), C (7)-N (2)-Zr (2) 165.5 (5) C (7)-N (2)-Zr (1) 93.0 (4), Zr (2)-N (2)-Zr (1) 99.7 (2), C (14)-N (3)-Zr (2) 166.2 (6), C (14)-N (3)-Zr (1) 92.1 (5), Zr (2)-N (3)-Zr (1) 100.3 (3), C (14)-N (4)-Zr (1) 90.6 (5) C (21)-N (4)-Zr (1) 142.2 (5), C (27)-O (1)-Zr (1) 124.6 (5), C (30)-O (1)-Zr (1) 125.1 (5), C (31)-O (2)-Zr (2) 124.4 (7), C (34)-O (2)-Zr (2) 128.9 (7), C (38)-O (3)-Zr (2) 123.2 (6) C (35)-O (3)-Zr (2) 129.5 (7), N (1)-C (7)-Zr (1) 57.8 (4), N (2)-C (7)-Zr (1) 57.1 (4), C (8)-C (7)-Zr (1) 175.0 (5), N (4)-C (14)-Zr (1) 59.9 (4), N (3)-C (14)-Zr (1) 57.6 (4) C (15)-C (14)-Zr (1) 168.2 (5) crystal parameter: chemical formula C
38h
56c
124n
4o
3zr
2, oblique system, spacer P2 (1)/n, unit cell parameters a=10.601 (4) Ab=17.226 (6) A c=24.093 (9) A α=90 °, β=96.936 (8) °, γ=90 °,
d
x=1.431g/cm
3, and Z=4, μ (Mo-K α)=0.760mm
-1, R
1=0.0671, wR
2=0.1604.Fig. 1 is shown in by the Single Crystal X-ray structure iron.
Embodiment 2
1. the preparation of catalyzer is with embodiment 1.
2. vinyl polymerization: the stainless steel still of 250 milliliters that mechanical stirring and thermocouple will be housed vacuumizes and uses nitrogen replacement 3 times, then with ethene displacement 2 times.Be warmed up to after 50 ℃, add successively toluene solution and a certain amount of toluene of catalyzer (4.9mg, 5 μ mol), then add methylaluminoxane (2.4mol/L, 1.04ml) making Al/Zr=500, the cumulative volume that finally adds a certain amount of toluene is 100 milliliters.Immediately the pressure of ethene is increased to 10 normal atmosphere, 50 ℃ of lower vigorous stirring 40 minutes.Reaction solution is poured out, added 5% ethanol solution hydrochloride neutralization, the adularescent solid is separated out, seasoning after filtering.Obtain product 0.4465 gram, polymerization activity: 1.33 * 10
5gmol (Zr)
-1h
-1.
Embodiment 3
1. the preparation of catalyzer is with embodiment 1.
2. vinyl polymerization: the stainless steel still of 250 milliliters that mechanical stirring and thermocouple will be housed vacuumizes and uses nitrogen replacement 3 times, then with ethene displacement 2 times.Be warmed up to after 50 ℃, add successively toluene solution and a certain amount of toluene of catalyzer 2a (4.8mg, 5 μ mol), then add methylaluminoxane (2.4mol/L, 2.1ml) making Al/Zr=1000, the cumulative volume that finally adds a certain amount of toluene is 100 milliliters.Immediately the pressure of ethene is increased to 10 normal atmosphere, 50 ℃ of lower vigorous stirring 40 minutes.Reaction solution is poured out, added 5% ethanol solution hydrochloride neutralization, the adularescent solid is separated out.Seasoning after filtering.Obtain product 0.6175 gram, polymerization activity: 1.84 * 10
5gmol (Zr)
-1h
-1.
Embodiment 4
1. the preparation of catalyzer is with embodiment 1.
2. vinyl polymerization: the stainless steel still of 250 milliliters that mechanical stirring and thermocouple will be housed vacuumizes and uses nitrogen replacement 3 times, then with ethene displacement 2 times.Be warmed up to after 50 ℃, add successively toluene solution and a certain amount of toluene of catalyzer 2a (4.8mg, 5 μ mol), then add methylaluminoxane (2.4mol/L, 3.2ml) making Al/Zr=1500, the cumulative volume that finally adds a certain amount of toluene is 100 milliliters.Immediately the pressure of ethene is increased to 10 normal atmosphere, 50 ℃ of lower vigorous stirring 40 minutes.Reaction solution is poured out, added 5% ethanol solution hydrochloride neutralization, the adularescent solid is separated out.Seasoning after filtering.Obtain product 0.6265 gram, polymerization activity: 1.87 * 10
5gmol (Zr)
-1h
-1.
Embodiment 5
1. the preparation of catalyzer is with embodiment 1.
2. vinyl polymerization: the stainless steel still of 250 milliliters that mechanical stirring and thermocouple will be housed vacuumizes and uses nitrogen replacement 3 times, then with ethene displacement 2 times.Be warmed up to after 50 ℃, add successively toluene solution and a certain amount of toluene of catalyzer (5.0mg, 5 μ mol), then add methylaluminoxane (2.4mol/L, 4.2ml) making Al/Zr=2000, the cumulative volume that finally adds a certain amount of toluene is 100 milliliters.Immediately the pressure of ethene is increased to 10 normal atmosphere, 50 ℃ of lower vigorous stirring 40 minutes.Reaction solution is poured out, added 5% ethanol solution hydrochloride neutralization, the adularescent solid is separated out.Seasoning after filtering.Obtain product 0.8427 gram, polymerization activity: 2.52 * 10
5gmol (Zr)
-1h
-1.
Embodiment 6
1. the preparation of catalyzer is with embodiment 1.
2. vinyl polymerization: the stainless steel still of 250 milliliters that mechanical stirring and thermocouple will be housed vacuumizes and uses nitrogen replacement 3 times, then with ethene displacement 2 times.Be warmed up to after 70 ℃, add successively toluene solution and a certain amount of toluene of catalyzer 2a (5.0mg, 5 μ mol), then add methylaluminoxane (2.4mol/L, 5.2ml) making Al/Zr=2500, the cumulative volume that finally adds a certain amount of toluene is 100 milliliters.Immediately the pressure of ethene is increased to 10 normal atmosphere, 50 ℃ of lower vigorous stirring 40 minutes.Reaction solution is poured out, added 5% ethanol solution hydrochloride neutralization, the adularescent solid is separated out.Seasoning after filtering.Obtain product 0.7244 gram, polymerization activity: 2.16 * 10
5gmol (Zr)
-1h
-1.
Claims (3)
1. two amidino groups Zr catalysts of a metal bridging is characterized in that structural formula is:
2. the preparation method of the two amidino groups Zr catalysts of a kind of metal bridging as claimed in claim 1, is characterized in that, comprises the steps:
Under the protection and ice-water bath of nitrogen, by hexahydroaniline and n-Butyl Lithium, according to 1: 1 hybrid reaction of mol ratio, solvent is tetrahydrofuran (THF), the 20-25 that its volume is the n-Butyl Lithium volume doubly, stirs, and naturally is warmed up to room temperature, keep stirring reaction 2-3 hour, obtain lithiated product solution, gained solution is placed under ice-water bath, then in above-mentioned solution, add the cyanobenzene that is equivalent to one times of mol ratio of lithiated product, stir, naturally be warmed up to room temperature, keep stirring reaction 5-6 hour, obtain adduct; Adduct is placed under ice-water bath again, add the zirconium tetrachloride that is equivalent to one times of mol ratio of previous step adduct, naturally be warmed up to room temperature, keep stirring reaction 5-6 hour, the product obtained is placed under ice-water bath again, adds the butyllithium of one times of mol ratio, naturally is warmed up to room temperature, keep stirring reaction 2-3 hour, obtain the two amidino groups Zr catalysts of metal bridging.
3. the two application of amidino groups Zr catalyst in vinyl polymerization of metal bridging as claimed in claim 1.
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