CN101798360A - Bridged diamidino group-IV metal catalyst and method for preparing same - Google Patents
Bridged diamidino group-IV metal catalyst and method for preparing same Download PDFInfo
- Publication number
- CN101798360A CN101798360A CN 201010144870 CN201010144870A CN101798360A CN 101798360 A CN101798360 A CN 101798360A CN 201010144870 CN201010144870 CN 201010144870 CN 201010144870 A CN201010144870 A CN 201010144870A CN 101798360 A CN101798360 A CN 101798360A
- Authority
- CN
- China
- Prior art keywords
- group
- bridged
- diamidino
- metal
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention provides a bridged diamidino group-IV metal catalyst, which relates to an olefin polymerization catalyst, in particular to a compound taking metals of a group IV as central atoms and a seven-element skeleton with an N-C-N-Si-N-C-N characteristic as a ligand. A method for preparing the bridged diamidino group-IV metal catalyst comprises the following steps: in the protection of nitrogen, taking bridging diamine as an initial raw material and converting the bridging diamine into a dilithium salt by utilizing butyl lithium; adding cyanophenyl into the dilithium salt to produce an addition reaction, forming a bridged diamidino ligand after migrating a silicon base twice, and performing a complex reaction on the polydentate ligand and group-IV metal chloride of the group IV to prepare bridged diamidino group-IV metal chloride; and reacting lithium methide with the bridged diamidino group-IV metal chloride to displace helium atoms to produce a methyl substitute. The synthesis method has the advantages of universal applicability, moderate reaction condition, simple and easily-obtained materials, low cost, simple steps and relatively higher productivity. The compound has good catalytic effect on the polyreaction of olefin.
Description
Technical field
The present invention relates to vinyl polymerization the 4th group 4 transition metal catalyzer, in particular to a kind of bridged diamidino group-IV metal catalyst and its production and application with N-C-N-Si-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 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.Defectives such as but, all there is the synthesis condition harshness in they, and the catalyzer total recovery is low, also have its catalyzer preservation condition also very harsh in addition, inactivation, and synthetic method complexity easily, 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 a class bridging, and had successfully explored its preparation route (Sheng-DiBai, Jian-Ping Guo, Dian-Sheng Liu, Dalton Trans., 2006,2244.).Further utilize this class part can synthesize the bridged diamidino group-IV metal compound, can access a class novel non-metallocene metal catalyst system, similar bridging is luxuriant on its node configuration, but it is advantageous that amidino groups is π
4Conjugated system, the π of the luxuriant ring of comparing
6Conjugated system electric density is less, and the substituting group pattern conversion is various, so this class of R and D is new and effective, the reaction conditions milder is easy to the bridged diamidino group-IV metal catalyst preserving and use, has practical value.
Summary of the invention
The object of the present invention is to provide a kind of bridged diamidino group-IV metal catalyst and preparation method thereof.
A kind of bridged diamidino group-IV metal catalyst provided by the invention has following structural formula:
The invention provides a kind of preparation method of bridged diamidino group-IV metal catalyst, comprise the steps:
(1) preparation of the two amidino groups part lithium salts of bridging: under protection of nitrogen gas and ice-water bath, with the silica-based bridging diamines of dimethyl and n-Butyl Lithium according to 1: 2 hybrid reaction of mol ratio, solvent is an ether, its volume is 10-15 a times of n-Butyl Lithium volume, stir, naturally be warmed up to room temperature, kept stirring reaction 2-3 hour, obtain the pairs of anion solution after the two lithiumations of diamines, gained solution is placed under the ice-water bath, the benzene nitrile that in above-mentioned solution, adds the silica-based bridging diamines of dimethyl twice as high molar ratio then, pairs of anion and benzene nitrile generation addition reaction obtain the two amidino groups part lithium salts of bridging;
1a：R＝Ph
1b：R＝2，6-Me
2Ph
1c：R＝2，6-
iPr
2Ph
1d：R＝
tBu
(2) the muriatic preparation of bridged diamidino group-IV metal: under protection of nitrogen gas; under acetone bath; be the 4th family's metal chloride to be joined in the two amidino groups part lithium salts of bridging in 1: 1 in molar ratio, solvent is tetrahydrofuran (THF) or ether, the amount of solvent be the two amidino groups part lithium salts weight of bridging 15-30 doubly; after solution is warmed up to room temperature naturally; kept stirring reaction 10-20 hour, vacuum is drained, and adds methylene dichloride; filter, filtrate concentrating obtained the bridged diamidino group-IV metal muriate.
2a：M＝Ti，R＝Ph
2b：M＝Ti，R＝2，6-Me
2Ph
2c：M＝Ti，R＝2，6-
iPr
2Ph
2d：M＝Ti，R＝
tBu
3a：M＝Zr，R＝Ph
3b：M＝Zr，R＝2，6-Me
2Ph
3c：M＝Zr，R＝2，6-
iPr
2Ph
3d：M＝Zr，R＝
tBu
4a：M＝Hf，R＝Ph
4b：M＝Hf，R＝2，6-Me
2Ph
4c：M＝Hf，R＝2，6-
iPr
2Ph
4d：M＝Hf，R＝
tBu
The invention provides the preparation method of another kind of bridged diamidino group-IV metal catalyst, comprise the steps:
(1) preparation of the two amidino groups part lithium salts of bridging is the same;
(2) the muriatic preparation of bridged diamidino group-IV metal, the same;
(3) under protection of nitrogen gas; the bridged diamidino group-IV metal muriate is dissolved in the tetrahydrofuran (THF) of 30 times of weight; under acetone bath; the lithium methide that adds bridged diamidino group-IV metal muriate twice as high molar ratio after solution is warmed up to room temperature naturally, kept stirring reaction 10-20 hour; vacuum is drained; add methylene dichloride, filter, filtrate concentrating obtained the bridged diamidino group-IV metal methyl substitute.
5a：M＝Ti，R＝Ph
5b：M＝Ti，R＝2，6-Me
2Ph
5c：M＝Ti，R＝2，6-
iPr
2Ph
5d：M＝Ti，R＝
tBu
6a：M＝Zr，R＝Ph
6b：M＝Zr，R＝2，6-Me
2Ph
6c：M＝Zr，R＝2，6-
iPr
2Ph
6d：M＝Zr，R＝
tBu
7a：M＝Hf，R＝Ph
7b：M＝Hf，R＝2，6-Me
2Ph
7c：M＝Hf，R＝2，6-
iPr
2Ph
7d：M＝Hf，R＝
tBu
Basic metal reagent with other carries out replacement(metathesis)reaction with similar method to chlorine, can prepare bridged diamidino group-IV metal alkyl substituent, aryl substituent, amino substituent, alkoxyl group substituent etc.
Bridged diamidino group-IV metal muriate, bridged diamidino group-IV metal methyl substitute all can be used as catalyzer and are applied to vinyl polymerization.
Synthetic catalyzer compared with prior art of the present invention is raw materials used to be easy to get, cheap, the preparation method is simple, and productive rate is higher; Bridged diamidino group-IV metal catalyst can be applied to vinyl polymerization, and the polymerization catalyst activity reaches as high as in the experiment of vinyl polymerization: 1.61 * 10
6Gmol (M)
-1H
-1, molecular weight of polyethylene can reach: 3.68 * 10
5Gmol
-1
Description of drawings
The crystalline structure figure of Fig. 1 1a
The crystalline structure figure of Fig. 2 1c
The crystalline structure figure of Fig. 3 1d
The crystalline structure figure of Fig. 4 2d
The crystalline structure figure of Fig. 5 3b
The crystalline structure figure of Fig. 6 3c
The crystalline structure figure of Fig. 7 3d
The crystalline structure figure of Fig. 8 4b
The crystalline structure figure of Fig. 9 4c
The crystalline structure figure of Figure 10 5d
Embodiment
The embodiment that only provides for explanation below, these embodiment are used to limit protection scope of the present invention.
(1) preparation of part lithium salts and sign
Under protection of nitrogen gas and under the ice-water bath, (6.0g 24.8mmol) is dissolved in ether (200cm with the silica-based bridging pentanoic of dimethyl
3) in, under agitation, add LiBu at leisure
nHexane solution (2.8mol dm
-3, 17.7cm
3, 49.6mmol), the question response mixed solution continues to stir 2 hours after returning to room temperature, and reaction solution is cooled to 0 ℃, adds PhCN (5.06cm with syringe
349.6mmol), the question response mixed solution continues to stir 5 hours after returning to room temperature, and the white solid matter that obtains after reaction is finished can obtain the two amidino groups part lithium salts 1a of yellow crystals shape bridging with the tetrahydrofuran (THF) recrystallization, Yield:17.2g (93%), mp 86-88 ℃.
1H NMR (300MHz, C
6D
6): δ 7.46-6.67 (m, 20H; Phenyls), 3.52 (t, J
HH=6.0Hz, 16H; OCH
2Of THF), 1.35 (p, J
HH=3.3,2.7Hz, 16H; 3,4-2CH
2Of THF), 0.24 (s, 3H; SiMe
2);
13CNMR (75MHz, C
6D
6): δ 175.7 (N-C-N), 154.0,143.8,132.5,132.4,127.1,126.6,125.3,121.3 (phenyls), 68.3 (OCH
2Of THF), 26.0 (3,4-2CH
2Of THF), 3.7 (SiMe
2) .Anal.Calc.forC
44H
58Li
2N
4O
4Si:C, 70.56; H, 7.81; N, 7.48%.Found:C, 70.16; H, 7.73; N, 7.60%.Crystalline structure is seen Fig. 1.
1b, the same 1a of the preparation condition of 1c and 1d, the data of their productive rate and sign thereof are as follows:
1b: colourless crystalline thing, Yield:90%, mp 136-138 ℃ of .Anal.Calc.for C
32H
34Li
2N
4Si (THF): C, 73.45; H, 7.19; N, 9.52%.Found:C, 72.86; H, 7.21; N, 9.44%.
1c: colourless crystalline thing, Yield:85%, 190 ℃ of decomposed.Anal.Calc.for C of mp
96H
132Li
4N
8O
4Si
2: C, 74.58; H, 8.61; N, 7.25%.Found:C, 74.29; H, 8.62; N, 7.42%.Crystalline structure is seen Fig. 2.
1d: colourless crystalline thing, Yield:82%, mp 177-179 ℃.
1H NMR (300MHz, C
6D
6): δ 7.29 (d, J
HH=1.8Hz, 8H; 2,6-H of phenyls), 7.11 (m, 12H; 3,4,5-H of phenyls), 1.34 (s, 36H; CMe
3) ,-0.13 (s, 12H; SiMe
2);
13C NMR (75MHz, C
6D
6): δ 175.4 (N-C-N), 143.1,127.3,127.0 (phenyls), 51.2 (CMe
3), 33.5 (CMe
3), 3.2 (SiMe
2);
7Li NMR (117MHz, C
6D
6): δ 2.27,2.02,1.85.Anal.Calc.forC
48H
68Li
4N
8Si
2: C, 68.55; H, 8.15; N, 13.32%.Found:C, 68.57; H, 8.18; N, 13.26%.Crystalline structure is seen Fig. 3.
(2) preparation of catalyzer 2d and sign
The Schlenk bottle is vacuumized logical N
2Replace after three times, (1.10g 1.32mmol) is dissolved in the ether (20mL), under-78 ℃ of agitation conditions, slowly adds TiCl to add ligand 1 d
4(thf)
2(0.88g, 2.64mmol), reaction mixture returns to room temperature gradually, continues to stir 12 hours.Under vacuum reaction solvent and volatilizable thing are drained, residuum dissolves with methylene dichloride (25mL), and extraction is filtered, and concentrated back placement for some time can grow scarlet lenticular compound 2d.Yield：1.11g(80％)，mp?194-195℃.
1H?NMR(300MHz，CD
6Cl
3)：δ7.83-7.14(m，10H；phenyls)，1.71-0.92(m，18H；
tBu)，0.41--0.27(m，6H；SiMe
2)；
13C?NMR(75MHz，CD
6Cl
3)：δ173.5，161.5(N-C-N)，139.2-128.8(phenyls)，59.5，58.1(CMe
3)，34.4，33.7，32.1，28.3(CMe
3)，8.3，4.0(SiMe
2).Anal.Calc.for?C
24H
34Cl
2N
4SiTi：C，54.86；H，6.52；N，10.66％.Found：C，54.41；H，6.57；N，10.24％。Crystalline structure is seen Fig. 4.
The preparation of catalyzer 3b and sign
(1) preparation of part lithium salts is with embodiment 1.
(2) the Schlenk bottle is vacuumized logical N
2Replace after three times, (1.43g 2.42mmol) with tetrahydrofuran (THF) 20mL, under-78 ℃ of agitation conditions, slowly adds ZrCl to add 1b
4(0.56g, 2.42mmol), reaction mixture returns to room temperature gradually, continues to stir 12 hours.Under vacuum reaction solvent and volatilizable thing are drained, residuum extracts and filters with methylene dichloride (25mL) dissolving, and decompression concentrates down, and placement for some time can grow flaxen lenticular compound 3b.Yield：1.02g(63％).M.p.：227～229℃.
1H?NMR(300MHz，CDCl
3)：δ7.33～6.83(m，16H；phenyls)，3.75(s，4H；OCH
2?of?THF)，2.30(s，12H；Me?on?phenyls)，1.54(s，4H；3，4-2CH
2?of?THF)，0.68(s，6H；SiMe
2)；
13C?NMR(75MHz，CDCl
3)：δ176.6(N-C-N)，147.0，137.7，135.4，133.3，131.3，130.6，130.1，126.7(phenyls)，76.0(OCH
2?of?THF)，27.3(3，4-2CH
2?of?THF)，22.5(Me?on?phenyls)，4.6(SiMe
2).Anal.Calc.for?C
36H
42Cl
2N
4OSiZr·(CH
2Cl
2)
0.25：C，57.42；H，5.65；N，7.39％.Found：C，57.26；H，5.56；N，7.26％。Crystalline structure is seen Fig. 5.
The preparation of catalyzer 3c and sign
(1) preparation of part lithium salts is with embodiment 1.
(2) the Schlenk bottle is vacuumized logical N
2Replace after three times, (1.31g 0.85mmol) with tetrahydrofuran (THF) 20mL, under-78 ℃ of agitation conditions, slowly adds ZrCl to add 1c
4(0.40g, 1.70mmol), reaction mixture returns to room temperature gradually, continues to stir 12 hours.Under vacuum reaction solvent and volatilizable thing are drained, residuum extracts and filters with methylene dichloride (25mL) dissolving, and decompression concentrates down, and placement for some time can grow colourless lenticular compound 3c.Yield：0.95g(66％).M.p.：256～257℃.
1H?NMR(300MHz，CDCl
3)：δ7.30～7.00(m，16H；phenyls)，3.82(t，4H；OCH
2?of?THF)，3.66(m，4H；CH(CH
3)
2)，1.58(p，4H；3，4-2CH
2?of?THF)，1.08，0.70(d，s，24H；CH(CH
3)
2)，0.75(s，6H；SiMe
2)；
13C?NMR(75MHz，CDCl
3)：δ175.0(N-C-N)，146.5，143.8，143.0，135.3，131.3，129.7，129.3，128.6，127.1，125.9，125.4，124.7(phenyls)，69.3(OCH
2?of?THF)，25.7(3，4-2CH
2?of?THF)，28.3，26.2，24.4(CH(CH
3)
2)，3.2(SiMe
2).Anal.Calc.forC
40H
50Cl
2N
4SiZr·(C
4H
8O)：C，62.23；H，6.88；N，6.60％.Found：C，61.86；H，6.79；N，6.76％。Crystalline structure is seen Fig. 6.
The preparation of catalyzer 3d and sign
(1) preparation of part lithium salts is with embodiment 1.
(2) the Schlenk bottle is vacuumized logical N
2Replace after three times, (0.76g 0.90mmol) with ether 20mL, under-78 ℃ of agitation conditions, slowly adds ZrCl to add 1d
4(0.42g, 1.80mmol), reaction mixture returns to room temperature gradually, continues to stir 12 hours.Under vacuum reaction solvent and volatilizable thing are drained, residuum extracts and filters with methylene dichloride (25mL) dissolving, and filtrate is drained, and uses the toluene recrystallization, and placement for some time can grow clear crystal shape compound 3d.Yield：0.83g(75％)。Crystalline structure is seen Fig. 7.
The preparation of catalyzer 4b and sign
(1) preparation of part lithium salts is with embodiment 1.
(2) the Schlenk bottle is vacuumized logical N
2Replace after three times, (1.30g 2.21mmol) with tetrahydrofuran (THF) 20mL, under-78 ℃ of agitation conditions, slowly adds HfCl to add 1b
4(0.71g, 2.21mmol), reaction mixture returns to room temperature gradually, continues to stir 12 hours.Under vacuum reaction solvent and volatilizable thing are drained, residuum extracts and filters with methylene dichloride (25mL) dissolving, and decompression concentrates down, and placement for some time can grow colourless lenticular compound 4b.Yield：0.95g(47％).M.p.：227～228℃.
1H?NMR(300MHz，CDCl
3)：δ7.32～6.82(m，16H；phenyls)，3.76(s，4H；OCH
2?of?THF)，2.31(s，12H；Me?on?phenyls)，1.52(s，4H；3，4-2CH
2?of?THF)，0.66(s，6H；SiMe
2)；
13C?NMR(75MHz，CDCl
3)：δ174.2(N-C-N)，145.2，136.8，134.1，131.6，130.6，129.1，128.7，125.1(phenyls)，74.7(OCH
2?of?THF)，25.8(3，4-2CH
2?of?THF)，20.9(Me?on?phenyls)，3.0(SiMe
2).Anal.Calc.for?C
36H
42Cl
2N
4OSiHf·(CH
2Cl
2)
0.75：C，49.71；H，4.94；N，6.31％.Found：C，49.76；H，5.09；N，5.97％。Crystalline structure is seen Fig. 8.
The preparation of catalyzer 4c and sign
(1) preparation of part lithium salts is with embodiment 1.
(2) the Schlenk bottle is vacuumized logical N
2Replace after three times, (0.75g 0.49mmol) with tetrahydrofuran (THF) 20mL, under-78 ℃ of agitation conditions, slowly adds HfCl to add 1c
4(0.31g, 0.98mmol), reaction mixture returns to room temperature gradually, continues to stir 12 hours.Under vacuum reaction solvent and volatilizable thing are drained, residuum extracts and filters with methylene dichloride (25mL) dissolving, and decompression concentrates down, and placement for some time can grow colourless lenticular compound 4c.Yield：0.52g(57％).M.p.：253～254℃.
1H?NMR(300MHz，CDCl
3)：δ7.29～7.02(m，16H；phenyls)，3.84(t，4H；OCH
2?of?THF)，3.68(m，4H；CH(CH
3)
2)，1.55(p，4H；3，4-2CH
2?of?THF)，1.14，0.68(d，s，24H；CH(CH
3)
2)，0.71(s，6H；SiMe
2)；
13C?NMR(75MHz，CDCl
3)：δ174.0(N-C-N)，143.9，142.7，135.9，131.1，129.3，128.8，128.6，128.4，125.8，125.1，124.5(phenyls)，68,8(OCH
2?of?THF)，25.8(3，4-2CH
2?of?THF)，28.2，26.0，24.3(CH(CH
3)
2)，3.2(SiMe
2).Anal.Calc.forC
40H
50Cl
2N
4SiHf·(C
4H
8O)：C，56.43；H，6.24；N，5.98％.Found：C，56.29；H，6.04；N，5.91％。Crystalline structure is seen Fig. 9.
The preparation of catalyzer 5d and sign
(1) preparation of 2d is with embodiment 1.
(2) the Schlenk bottle is vacuumized logical N
2Replace after three times, (0.83g 1.58mmol) with ether 20mL, under-78 ℃ of agitation conditions, slowly adds LiMe (1.6mol dm to add 2d
-3, 1.98cm
3, 3.16mmol), reaction mixture returns to room temperature gradually, continues to stir 12 hours.Under vacuum reaction solvent and volatilizable thing are drained, residuum dissolves with methylene dichloride (20mL), and extraction is filtered, and concentrated back placement for some time can grow yellow crystals shape compound 5d.Yield：0.38g(50％).
1H?NMR(300MHz，CD
6Cl
3)：δ7.38(p，10H；phenyls)，1.44，1.41(d，18H；
tBu)，1.08(s，6H；TiMe
2)，-0.21(s，6H；SiMe
2)；
13C?NMR(75MHz，CD
6Cl
3)：δ171.4(N-C-N)，142.0(ipso-C?ofphenyl)，131.0-129.0(phenyls)，66.8(TiMe
2)，58.0(CMe
3)，35.2，34.8(CMe
3)，4.5(SiMe
2).。Crystalline structure is seen Figure 10.
1. the preparation of catalyzer 2d is with embodiment 1.
2. vinyl polymerization: 250 milliliters the stainless steel still that mechanical stirring and thermocouple will be housed vacuumizes and uses N while hot 130 ℃ of successive dryings 6 hours
2Gas displacement 3 times.Add catalyzer 2d (2.6mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (25.0ml) with syringe, (1.46mol/L 51ml) makes Al/Ti=15000, and the cumulative volume of toluene is 100 milliliters to add the toluene solution of methylaluminoxane (MAO) again.Under 100 ℃, the pressure with ethene is increased to 10 normal atmosphere immediately, vigorous stirring 30 minutes.The ethanol solution hydrochloride of adding 5% neutralization in the reaction solution, the adularescent solid is separated out.Filtered final vacuum dry 12 hours.Obtain product 2.55 grams, polymerization activity: 1.02 * 10
6Gmol (Ti)
-1H
-1, the fusing point of polymkeric substance: 133.1 ℃, molecular weight: 3.68 * 10
5Gmol
-1, molecular weight distribution: 14.3.
1. the preparation of catalyzer 3c is with embodiment 3.
2. vinyl polymerization: 250 milliliters the stainless steel still that mechanical stirring and thermocouple will be housed vacuumizes and uses N while hot 130 ℃ of successive dryings 6 hours
2Gas displacement 3 times.Add catalyzer 3c (4.2mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (25.0ml) with syringe, (1.46mol/L 3.4ml) makes Al/Zr=1000, and the cumulative volume of toluene is 100 milliliters to add the toluene solution of methylaluminoxane (MAO) again.Under 30 ℃, the pressure with ethene is increased to 10 normal atmosphere immediately, vigorous stirring 30 minutes.The ethanol solution hydrochloride of adding 5% neutralization in the reaction solution, the adularescent solid is separated out.Filtered final vacuum dry 12 hours.Obtain product 0.542 gram, polymerization activity: 2.16 * 10
5Gmol (Zr)
-1H
-1
1. the preparation of catalyzer 3c is with embodiment 3.
2. vinyl polymerization: 250 milliliters the stainless steel still that mechanical stirring and thermocouple will be housed vacuumizes and uses N while hot 130 ℃ of successive dryings 6 hours
2Gas displacement 3 times.Add catalyzer 3c (4.2mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (25.0ml) with syringe, (1.46mol/L 3.4ml) makes Al/Zr=1000, and the cumulative volume of toluene is 100 milliliters to add the toluene solution of methylaluminoxane (MAO) again.Under 50 ℃, the pressure with ethene is increased to 10 normal atmosphere immediately, vigorous stirring 30 minutes.The ethanol solution hydrochloride of adding 5% neutralization in the reaction solution, the adularescent solid is separated out.Filtered final vacuum dry 12 hours.Obtain product 1.46 grams, polymerization activity: 5.84 * 10
5Gmol (Zr)
-1H
-1
1. the preparation of catalyzer 4c is with embodiment 6.
2. vinyl polymerization: 250 milliliters the stainless steel still that mechanical stirring and thermocouple will be housed vacuumizes and uses N while hot 130 ℃ of successive dryings 6 hours
2Gas displacement 3 times.Add catalyzer 4c (4.7mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (25.0ml) with syringe, (1.46mol/L 3.4ml) makes Al/Hf=1000, and the cumulative volume of toluene is 100 milliliters to add the toluene solution of methylaluminoxane (MAO) again.Under 50 ℃, the pressure with ethene is increased to 10 normal atmosphere immediately, vigorous stirring 30 minutes.The ethanol solution hydrochloride of adding 5% neutralization in the reaction solution, the adularescent solid is separated out.Filtered final vacuum dry 12 hours.Obtain product 1.32 grams, polymerization activity: 5.27 * 10
5Gmol (Hf)
-1H
-1
1. the preparation of catalyzer 5d is with embodiment 7.
2. vinyl polymerization: 250 milliliters the stainless steel still that mechanical stirring and thermocouple will be housed vacuumizes and uses N while hot 130 ℃ of successive dryings 6 hours
2Gas displacement 3 times.Add catalyzer 5d (2.4mg, 5 μ mol), and then vacuumize and replace 2 times with ethene.Inject a certain amount of toluene (25.0ml) with syringe, (1.46mol/L 51ml) makes Al/Ti=15000, and the cumulative volume of toluene is 100 milliliters to add the toluene solution of methylaluminoxane (MAO) again.Under 80 ℃, the pressure with ethene is increased to 10 normal atmosphere immediately, vigorous stirring 30 minutes.The ethanol solution hydrochloride of adding 5% neutralization in the reaction solution, the adularescent solid is separated out.Filtered final vacuum dry 12 hours.Obtain product 4.04 grams, polymerization activity: 1.61 * 10
6Gmol (Ti)
-1H
-1, the fusing point of polymkeric substance: 133.9 ℃, molecular weight: 1.07 * 10
5Gmol
-1, molecular weight distribution: 3.60.
Claims (4)
1. a bridged diamidino group-IV metal catalyst is characterized in that, has following structural formula:
2. the preparation method of a kind of bridged diamidino group-IV metal catalyst as claimed in claim 1 is characterized in that, comprises the steps:
(1) preparation of the two amidino groups part lithium salts of bridging;
(2) the muriatic preparation of bridged diamidino group-IV metal: under protection of nitrogen gas; under acetone bath; be the 4th family's metal chloride to be joined in the two amidino groups part lithium salts of bridging in 1: 1 in molar ratio, solvent is tetrahydrofuran (THF) or ether, the amount of solvent be the two amidino groups part lithium salts weight of bridging 15-30 doubly; after solution is warmed up to room temperature naturally; kept stirring reaction 10-20 hour, vacuum is drained, and adds methylene dichloride; filter, filtrate concentrating obtained the bridged diamidino group-IV metal muriate.
3. the preparation method of a kind of bridged diamidino group-IV metal catalyst as claimed in claim 2; it is characterized in that; comprise step (3); promptly under protection of nitrogen gas; the bridged diamidino group-IV metal muriate is dissolved in the tetrahydrofuran (THF) of 30 times of weight; under acetone bath; the lithium methide that adds bridged diamidino group-IV metal muriate twice as high molar ratio; after solution is warmed up to room temperature naturally; kept stirring reaction 10-20 hour, vacuum is drained, and adds methylene dichloride; filter, filtrate concentrating obtained the bridged diamidino group-IV metal methyl substitute.
4. the application of bridged diamidino group-IV metal catalyst as claimed in claim 1 in olefinic polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010144870 CN101798360A (en) | 2010-04-08 | 2010-04-08 | Bridged diamidino group-IV metal catalyst and method for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010144870 CN101798360A (en) | 2010-04-08 | 2010-04-08 | Bridged diamidino group-IV metal catalyst and method for preparing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101798360A true CN101798360A (en) | 2010-08-11 |
Family
ID=42594217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010144870 Pending CN101798360A (en) | 2010-04-08 | 2010-04-08 | Bridged diamidino group-IV metal catalyst and method for preparing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101798360A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311539A (en) * | 2011-07-09 | 2012-01-11 | 山西大学 | Trinuclear organic zinc catalyst, and preparation method and application thereof |
| CN102321236A (en) * | 2011-06-21 | 2012-01-18 | 山西大学 | Bridged diamidine-based zinc catalyst and preparation method and application thereof |
| CN102432700A (en) * | 2011-09-01 | 2012-05-02 | 山西大学 | Bridged diamidino titanium metal catalyst, and preparation method and application thereof |
| CN102603935A (en) * | 2012-02-24 | 2012-07-25 | 山西大学 | Metal bridging bis-guanyl zirconium catalyst and preparation method and application thereof |
| CN102659965A (en) * | 2012-05-11 | 2012-09-12 | 山西大学 | Amidino group 4 metal catalyst, and preparation method and application thereof |
| 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 |
| CN105482007A (en) * | 2016-01-08 | 2016-04-13 | 山西大学 | Bis-diimine silicon-bridged zirconium catalyst and preparation method thereof |
| CN105646749A (en) * | 2016-01-08 | 2016-06-08 | 山西大学 | Beta-diiminosilicon bridged dimethylamino zirconium catalyst and preparation thereof |
-
2010
- 2010-04-08 CN CN 201010144870 patent/CN101798360A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 《中国博士学位论文全文数据库工程科技I辑》 20061031 白生弟 硅桥联双脒基金属化合物的合成和硅基取代甲基锂与腈的反应研究 B014-3 1-4 , 第10期 2 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321236A (en) * | 2011-06-21 | 2012-01-18 | 山西大学 | Bridged diamidine-based zinc catalyst and preparation method and application thereof |
| CN102311539B (en) * | 2011-07-09 | 2012-07-25 | 山西大学 | Trinuclear organic zinc catalyst, and preparation method and application thereof |
| CN102311539A (en) * | 2011-07-09 | 2012-01-11 | 山西大学 | Trinuclear organic zinc catalyst, and preparation method and application thereof |
| CN102432700A (en) * | 2011-09-01 | 2012-05-02 | 山西大学 | Bridged diamidino titanium metal catalyst, and preparation method and application thereof |
| CN102603935B (en) * | 2012-02-24 | 2013-06-05 | 山西大学 | Metal bridging bis-guanyl zirconium catalyst and preparation method and application thereof |
| CN102603935A (en) * | 2012-02-24 | 2012-07-25 | 山西大学 | Metal bridging bis-guanyl zirconium catalyst and preparation method and application thereof |
| CN102659965A (en) * | 2012-05-11 | 2012-09-12 | 山西大学 | Amidino group 4 metal catalyst, and preparation method and application thereof |
| CN102659965B (en) * | 2012-05-11 | 2014-01-01 | 山西大学 | Amidino group 4 metal catalyst, and preparation method and application thereof |
| 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 |
| CN105482007A (en) * | 2016-01-08 | 2016-04-13 | 山西大学 | Bis-diimine silicon-bridged zirconium catalyst and preparation method thereof |
| CN105646749A (en) * | 2016-01-08 | 2016-06-08 | 山西大学 | Beta-diiminosilicon bridged dimethylamino zirconium catalyst and preparation thereof |
| CN105646749B (en) * | 2016-01-08 | 2017-11-03 | 山西大学 | Beta diimine silicon bridge dimethylamino Zr catalyst and its preparation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101798360A (en) | Bridged diamidino group-IV metal catalyst and method for preparing same | |
| CN106750227B (en) | A kind of catalyst system for the ring-opening polymerization of lactone by catalysis that activity is controllable | |
| CN105237552A (en) | Oxazoline ring-containing amino tocopheroxyl zinc/magnesium complexes and preparation method and application thereof | |
| Bai et al. | Diverse coordination behaviors of the silyl-linked bis (amidinate) ligand [SiMe2 {NC (Ph) N (Ph)} 2] 2− to zirconium center | |
| Forret et al. | Multistep Self-Assembly of Heteroleptic Magnesium and Sodium− Magnesium Benzamidinate Complexes | |
| Wang et al. | Homolysis of the Eu− N Bond. Synthesis, Structural Characterization, and Catalytic Activity of Novel Europium (II) Complexes | |
| Okuda et al. | Chiral complexes of titanium containing a linked amido-cyclopentadienyl ligand: synthesis, structure, and asymmetric imine hydrogenation catalysis | |
| Ho et al. | Synthesis of zirconocene phosphinidenes and phosphides via phosphorus-hydrogen activation | |
| CN101786018B (en) | Amino-silicone bridge nitrogen-blending allyl zirconium catalyst and preparation method and application thereof | |
| Bai et al. | An alkyl-ended ansa-bis (amidine) and solvent-influenced complexation modes of its group IV metal derivatives | |
| Cole et al. | Coordinative versatility in main group complexes of C-2, 6-terphenyl substituted amidinates | |
| CN105273000A (en) | Asymmetric constrained-geometry dinuclear metallocene compound and preparation method and application thereof | |
| CN105418672B (en) | One kind is containing big empty complex for hindering [O, N, O] tridentate ligand titanium, zirconium of bis aryloxy and application thereof | |
| CN103189397B (en) | Catalyst for norbornene monomer polymerization and method for producing norbornene polymer | |
| Roesky | Cyclooctatetraene complexes of yttrium and the lanthanides with chiral and achiral aminotroponiminates | |
| CN102603935B (en) | Metal bridging bis-guanyl zirconium catalyst and preparation method and application thereof | |
| CN101357931A (en) | Imino-1,10-phenanthroline chromium dichloride complex, preparation method and application thereof | |
| CN107098992B (en) | Cyclic annular multicore salicylic alidehyde imine nickel-metal catalyst precursor and its preparation and application | |
| Álvarez-Vergara et al. | Flexible Building Blocks for Transition Metal Early− Late Chemistry. Synthesis of Heterobimetallic Tetranuclear Metallomacrocycles | |
| CN103304690A (en) | Bridged bis cobalt amidinate lithium mixed metal catalyst, and preparation method and application thereof | |
| Schulz et al. | Syntheses and x-ray structures of novel main group bis (dialkylamino) phosphinimides | |
| Ramos et al. | [(Allylsilyl)(η-amidosilyl)-η5-cyclopentadienyl] Group 4 Metal Complexes: Synthesis, Reactivity, and Olefin Polymerization | |
| Le Gendre et al. | Synthesis and structural studies of Ti Ru polymetallic systems | |
| US20110137060A1 (en) | Preparation of ansa metallocene compounds | |
| Banda | The Application of the 10-Vertex closo-Carborane Anion in N-Heterocyclic Carbenes and Iridium Complexes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20100811 |