CN102603935A - 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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- CN102603935A CN102603935A CN2012100445167A CN201210044516A CN102603935A CN 102603935 A CN102603935 A CN 102603935A CN 2012100445167 A CN2012100445167 A CN 2012100445167A CN 201210044516 A CN201210044516 A CN 201210044516A CN 102603935 A CN102603935 A CN 102603935A
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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.
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 through the structure of regulating part.Brintzinger has reported that one type of 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.Defectives such as but, they all exist synthesis condition harsh, and the catalyzer total recovery is low; Also have its catalyzer preservation condition also very harsh in addition, inactivation, and compound method easily is complicated; Shortcomings such as raw material should not prepare, thereby the novel non-metallocene metal catalyst becomes the focus of Recent study.Not long ago our study group had designed the two amidino groups parts of one type of bridging, and had successfully explored its preparation route (Sheng-Di Bai, Jian-Ping Guo, Dian-Sheng Liu; Dalton Trans., 2006,2244.); Further utilize this type part to synthesize the bridged diamidino group-IV metal compound, can access one type of novel non-metallocene metal catalyst system, similar bridging is luxuriant on its node configuration; But it is advantageous that the substituting group pattern conversion is various, the reaction conditions milder is easy to preserve; Have two active centers, so the new and effective two amidino groups Zr catalysts of metal bridging of this type of R and D have 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, and reaction conditions is gentle, and raw material is easy to get, and is used for vinyl polymerization and has good catalytic activity.
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 comprises the steps:
Under protection of nitrogen gas and ice-water bath, according to 1: 1 hybrid reaction of mol ratio, solvent is a THF with hexahydroaniline and n-Butyl Lithium, its volume be the n-Butyl Lithium volume 20-25 doubly; Stir, be warmed up to room temperature naturally, kept stirring reaction 2-3 hour, obtain lithiated product solution; Gained solution is placed under the ice-water bath, in above-mentioned solution, add the cyanobenzene that is equivalent to one times of mol ratio of lithiated product then, stir; Naturally be warmed up to room temperature, kept stirring reaction 5-6 hour, obtain adduct; Adduct places under the ice-water bath again, adds the zirconium tetrachloride that is equivalent to one times of mol ratio of a step adduct, is warmed up to room temperature naturally; Kept stirring reaction 5-6 hour; The product that obtains places under the ice-water bath again, adds the butyllithium of one times of mol ratio, is warmed up to room temperature naturally; Keep stirring reaction 2-3 hour, and obtained the two amidino groups Zr catalysts of metal bridging.
Advantage compared with prior art of the present invention and effect: synthetic catalyst of the present invention is raw materials used be simple and easy to, cheap, the preparation method is simple, and productive rate is higher, has two active centers; Catalyzer is used for vinyl polymerization has advantages of high catalytic activity.
Description of drawings
The monocrystalline X-ray structure diagram of the two amidino groups Zr catalysts of Fig. 1 metal bridging of the present invention
Embodiment
Below only for specifying the specific embodiment that the present invention provides, these embodiment are used to limit protection scope of the present invention.
Embodiment 1 Preparation of catalysts and sign
(1) preparation of the two amidino groups Zr catalysts of metal bridging
Under protection of nitrogen gas and ice-water bath, (0.68ml 5.88mmol) is dissolved in THF (15cm with hexahydroaniline
3) in, under agitation, add the hexane solution (2.2moldm of butyllithium at leisure
-3, 2.67cm
3, 5.88mmol), the question response mixed solution returns to the room temperature continued and stirred 2 hours, and reaction solution is cooled to 0 ℃; With syringe add the benzene nitrile (0.59cm3,5.88mmol), the question response mixed solution returns to the room temperature continued and stirred 5 hours; Again reaction solution is cooled to 0 ℃, and the adding zirconium tetrachloride (1.43g, 5.88mmol); The question response mixed solution returns to the room temperature continued and stirred 5 hours, and reaction solution is cooled to 0 ℃, adds the hexane solution (2.2moldm of butyllithium at leisure
-3, 2.67cm
3, 5.88mmol), the question response mixed solution returns to the room temperature continued and stirred 2 hours; Reaction is drained after finishing, and the solid matter that obtains dissolves with toluene, filters; Filtrating is added a small amount of THF after concentrating, and 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.The monocrystalline X-ray structure diagram is seen Fig. 1.
Embodiment 2
1. Preparation of catalysts is with embodiment 1.
2. vinyl polymerization: 250 milliliters the stainless steel still that mechanical stirring and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.Be warmed up to after 50 ℃, add toluene solution and a certain amount of toluene of catalyzer (4.9mg, 5 μ mol) successively, (2.4mol/L 1.04ml) makes Al/Zr=500, and the TV that adds a certain amount of toluene at last is 100 milliliters to add MAO again.Pressure with ethene was increased to 10 normal atmosphere immediately, 50 ℃ of following vigorous stirring 40 minutes.Reaction solution is poured out, added 5% ethanol solution hydrochloride neutralization, the adularescent solid is separated out, and filters the back seasoning.Obtain product 0.4465 gram, polymerization activity: 1.33 * 10
5Gmol (Zr)
-1H
-1
Embodiment 3
1. Preparation of catalysts is with embodiment 1.
2. vinyl polymerization: 250 milliliters the stainless steel still that mechanical stirring and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.Be warmed up to after 50 ℃, add toluene solution and a certain amount of toluene of catalyzer 2a (4.8mg, 5 μ mol) successively, (2.4mol/L 2.1ml) makes Al/Zr=1000, and the TV that adds a certain amount of toluene at last is 100 milliliters to add MAO again.Pressure with ethene was increased to 10 normal atmosphere immediately, 50 ℃ of following vigorous stirring 40 minutes.Reaction solution is poured out, added 5% ethanol solution hydrochloride neutralization, the adularescent solid is separated out.Filter the back seasoning.Obtain product 0.6175 gram, polymerization activity: 1.84 * 10
5Gmol (Zr)
-1H
-1
Embodiment 4
1. Preparation of catalysts is with embodiment 1.
2. vinyl polymerization: 250 milliliters the stainless steel still that mechanical stirring and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.Be warmed up to after 50 ℃, add toluene solution and a certain amount of toluene of catalyzer 2a (4.8mg, 5 μ mol) successively, (2.4mol/L 3.2ml) makes Al/Zr=1500, and the TV that adds a certain amount of toluene at last is 100 milliliters to add MAO again.Pressure with ethene was increased to 10 normal atmosphere immediately, 50 ℃ of following vigorous stirring 40 minutes.Reaction solution is poured out, added 5% ethanol solution hydrochloride neutralization, the adularescent solid is separated out.Filter the back seasoning.Obtain product 0.6265 gram, polymerization activity: 1.87 * 10
5Gmol (Zr)
-1H
-1
Embodiment 5
1. Preparation of catalysts is with embodiment 1.
2. vinyl polymerization: 250 milliliters the stainless steel still that mechanical stirring and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.Be warmed up to after 50 ℃, add toluene solution and a certain amount of toluene of catalyzer (5.0mg, 5 μ mol) successively, (2.4mol/L 4.2ml) makes Al/Zr=2000, and the TV that adds a certain amount of toluene at last is 100 milliliters to add MAO again.Pressure with ethene was increased to 10 normal atmosphere immediately, 50 ℃ of following vigorous stirring 40 minutes.Reaction solution is poured out, added 5% ethanol solution hydrochloride neutralization, the adularescent solid is separated out.Filter the back seasoning.Obtain product 0.8427 gram, polymerization activity: 2.52 * 10
5Gmol (Zr)
-1H
-1
Embodiment 6
1. Preparation of catalysts is with embodiment 1.
2. vinyl polymerization: 250 milliliters the stainless steel still that mechanical stirring and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, again with ethene displacement 2 times.Be warmed up to after 70 ℃, add toluene solution and a certain amount of toluene of catalyzer 2a (5.0mg, 5 μ mol) successively, (2.4mol/L 5.2ml) makes Al/Zr=2500, and the TV that adds a certain amount of toluene at last is 100 milliliters to add MAO again.Pressure with ethene was increased to 10 normal atmosphere immediately, 50 ℃ of following vigorous stirring 40 minutes.Reaction solution is poured out, added 5% ethanol solution hydrochloride neutralization, the adularescent solid is separated out.Filter the back seasoning.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 protection of nitrogen gas and ice-water bath, according to 1: 1 hybrid reaction of mol ratio, solvent is a THF with hexahydroaniline and n-Butyl Lithium, its volume be the n-Butyl Lithium volume 20-25 doubly; Stir, be warmed up to room temperature naturally, kept stirring reaction 2-3 hour, obtain lithiated product solution; Gained solution is placed under the ice-water bath, in above-mentioned solution, add the cyanobenzene that is equivalent to one times of mol ratio of lithiated product then, stir; Naturally be warmed up to room temperature, kept stirring reaction 5-6 hour, obtain adduct; Adduct places under the ice-water bath again, adds the zirconium tetrachloride that is equivalent to one times of mol ratio of a step adduct, is warmed up to room temperature naturally; Kept stirring reaction 5-6 hour; The product that obtains places under the ice-water bath again, adds the butyllithium of one times of mol ratio, is warmed up to room temperature naturally; Keep stirring reaction 2-3 hour, and obtained 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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333277A (en) * | 2013-06-21 | 2013-10-02 | 山西大学 | Diamidino methoxyl bridged dual-core zirconium catalyst as well as preparation method and application thereof |
| CN105837716A (en) * | 2016-04-07 | 2016-08-10 | 山西大学 | Mixed amidino amino IV-group metal catalysts, and preparing method and applications thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005090418A1 (en) * | 2004-03-17 | 2005-09-29 | Dsm Ip Assets B.V. | Polimerization catalyst comprising an amidine ligand |
| CN101798360A (en) * | 2010-04-08 | 2010-08-11 | 山西大学 | Bridged diamidino group-IV metal catalyst and method for preparing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005090418A1 (en) * | 2004-03-17 | 2005-09-29 | Dsm Ip Assets B.V. | Polimerization catalyst comprising an amidine ligand |
| CN101798360A (en) * | 2010-04-08 | 2010-08-11 | 山西大学 | Bridged diamidino group-IV metal catalyst and method for preparing same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333277A (en) * | 2013-06-21 | 2013-10-02 | 山西大学 | Diamidino methoxyl bridged dual-core zirconium catalyst as well as preparation method and application thereof |
| CN103333277B (en) * | 2013-06-21 | 2015-09-30 | 山西大学 | Two amidino groups methoxyl group bridged binuclear Zr catalyst and its preparation method and application |
| CN105837716A (en) * | 2016-04-07 | 2016-08-10 | 山西大学 | Mixed amidino amino IV-group metal catalysts, and preparing method and applications thereof |
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