CN101492390A - Novel three-tooth nitrogen ligand and rare earth metal complex - Google Patents

Novel three-tooth nitrogen ligand and rare earth metal complex Download PDF

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CN101492390A
CN101492390A CNA2009100471827A CN200910047182A CN101492390A CN 101492390 A CN101492390 A CN 101492390A CN A2009100471827 A CNA2009100471827 A CN A2009100471827A CN 200910047182 A CN200910047182 A CN 200910047182A CN 101492390 A CN101492390 A CN 101492390A
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CN101492390B (en
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陈耀峰
陆而立
甘伟
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

The invention relates to a novel tridentate nitrogen ligand, rare earth metal complexes thereof and the application of the rare earth metal complexes in the olefin hydroamination reaction and the polyester synthesis. The ligand of the kind can be obtained from corresponding beta diketone and amine by two-step condensation reaction; the rare earth complexes can be obtained by the reaction between the ligand and rare earth metal alkyl and amidine compounds. The rare earth complexes can effectively catalyze the olefin hydroamination reaction and the ring-opening polymerization of lactones. The structural general formulas of the tridentate nitrogen and the corresponding rare earth complexes are shown as above.

Description

Novel three-tooth nitrogen ligand and rare earth metal complex thereof
Technical field:
The present invention relates to a class novel three-tooth nitrogen ligand and rare earth metal complex thereof and the application in alkene hydroamination reaction and lactone ring opening polymerization.
Technical background:
In recent years, in numerous organic reactions and macromolecular synthetic reaction, rare earth metal complex has all shown good catalytic activity.Wherein, research is the cyclopentadienyl rare-earth metal complex compound that contains cyclopentadiene base class part the most widely.But the synthetic cost of this type of complex compound is higher.Therefore, people have studied numerous non-luxuriant type rare earth metal complexes that do not contain cyclopentadienyl.In non-luxuriant type rare earth metal complex, containing n-donor ligand occupies an important position.Containing n-donor ligand generally be easy to synthetic and cost lower, and rare earth metal-nitrogen key be formed with help stable have high Electron Affinities, high reaction activity rare earth compound.In a series of containing n-donor ligands, the most potential is beta diimine ligand.This class part can be obtained by corresponding beta diketone and amine condensation, and is synthetic simple; Simultaneously, the stereoeffect of this type of part and electronic effect can be easily by selecting suitable starting raw material to regulate and control; In addition, the coordination mode of beta diimine class part and rare earth metal is various, both can be that pure σ key also can be the combination of σ key and π key.In the last few years, people had synthesized a large amount of beta diimine-rare earth metal complexes, and some complex compounds have wherein shown good catalytic activity in polyreaction and organic molecule reaction.The for example ring-opening polymerization of catalysis caprolactone or rac-Lactide, methyl methacrylate polymerization, vinyl polymerization, the copolymerization of cyclohexene oxide and carbonic acid gas, the dimerization reaction of intramolecularly hydroamination reaction and alkynes etc.In these complex compounds, rare earth metal alkyl compound contains highly active rare earth metal-C (σ) key and makes concern especially owing to it.For beta diimine-rare earth metal alkyl compound, in the ion of having reported, be the two alkylates that contain two alkyl.
People such as Warren E.Piers have reported two alkylates (Hayes, the P.G. of following several small ion radius metal Sc; Lee, L.W.M.; Knight, L.K.; Piers, W.E.; Parvez, M.; Elsegood, M.R.J.; Clegg, W.; MacDonald, R.Organometallics 2001,20, and 2533.).The complex structure formula is as follows:
Figure A20091004718200061
R＝CH 3， tBu
R’＝CH 3，CH 2CH 3，CH 2C 6H 5，CH 2 tBu，CH 2TMS
People such as Michael F.Lappert have reported two alkylates of a Ce, but that its usefulness is the big sterically hindered alkyl-CH of low activity (TMS) 2(Hitchcock, P.B.; Lappert, M.F.; Tian, S.J.Chem.Soc., Dalton Trans.1997,1945.).Complex structure is as follows:
Figure A20091004718200062
R＝CH(TMS) 2
By introducing two symmetric nitrogenous side chains of giving body, Herbert W.Roesky etc. has designed and synthesized a tetradentate ligands, synthesized a series of solvent or the solvent-free rare-earth metal chloride of containing simultaneously, but it is very difficult during the synthesis of alkyl compound, they have only reported synthetic (Neculai, the D. of the two alkylates of beta diimine Tb; Roesky, H.W.; Neculai, A.M.; Magull, J.; Herbst-Irmer, R.; Walfort, B.; Stalke, D.Organometallics 2003,22, and 2279.).Ligand structure is as follows:
Figure A20091004718200063
In our previous work, synthesized on a series of one side N aromatic group has been arranged, the beta diimine class three tooth nitrogen single anion ligands that the coordination side chain is arranged on the other side N, and two alkylates of a series of rare earth metals based on this part and diamine based compounds have been synthesized, wherein three-tooth nitrogen ligand plays single anion ligand effect (Xu, X.; Xu, X.Y.; Chen, Y.F.; Sun, J.Organometallics 2008,27, and 758; Chinese patent application prospectus CN101186617).Part and complex structure are as follows:
Figure A20091004718200071
RE＝Y，Lu，Sm，Nd
These rare earth metal complexs can high reactivity ground catalyzing lactone polyreaction.
More than two alkyl and diamine based compound very high as catalyst activity, but the some shortcomings part is arranged also.It has two initiating groups, thus when catalyzed reaction three-dimensional controllability a little less than.One of way that addresses this problem is to obtain a class can play the effect of dianion part in metal complexes novel three-tooth nitrogen ligand, and synthetic rare earth metal monoalkyl and the monoamine based compound that has only an initiating group.
The N-H key is the synthetic important method that contains the N compound to the hydroamination reaction of carbon carbon unsaturated link(age) (as C=C, C ≡ C, C=C=C etc.), and it is extensively to exist in natural product and medicine that this class contains the N compound.Therefore, this type of hydroamination reaction is an important field of research always.People have studied a lot of these type of reactions of different catalysts, as Bronsted acid, basic metal, alkaline-earth metal, preceding transition and late transition metal catalyst.In these catalyzer, rare-earth metal catalyst has advantages of high catalytic activity, receives bigger concern in recent years.
In recent years, when macromolecular material brings convenience to people's lives,, caused the serious environmental pollution problem after discarding because of its most of material does not possess biodegradable characteristic.At present the processing means of non-degradable goods are buried often and burned, do like this and can only alleviate environmental pollution.And the application of degradable high polymer material can fundamentally address this problem.Simultaneously, over nearly 20 years, increasing clinical needs have promoted the development of bio-medical material, the focus that the polymer materials of synthesized degradable has become current biomaterial research and used.The biodegradation type medical macromolecular materials mainly comprise polyester, poly-acid anhydrides, polyamino acid, poly-phosphorus cyanogen etc.Wherein aliphatic polyester is with its good biocompatibility, biological degradability, and advantages such as polymkeric substance and degraded product nontoxicity enjoy common people to pay close attention to.Aliphatic polyester generally prepares by ring-opening polymerization.
Summary of the invention:
The present invention is based on sterically hindered and consideration ligancy, designed and synthesized a series of novel three-tooth nitrogen ligands (this class three-tooth nitrogen ligand can play the effect of dianion part in metal complexes) and rare earth metal complex thereof a metal-organic complex.
The purpose of this invention is to provide a class novel three-tooth nitrogen ligand and a rare earth metal complex thereof.
Another object of the present invention provides the synthetic method of synthetic above-mentioned part and rare earth metal complex thereof.
The present invention also provides the application of above-mentioned rare earth metal complex in hydroamination reaction and polyester are synthetic.
Described containing n-donor ligand can be the intermediate of rare earth metal complex, and its structure is as follows:
Figure A20091004718200081
The structure of described rare earth metal complex is as follows:
Figure A20091004718200082
Wherein, R 1Be C 1-10Alkyl, R 2Be H, halogen or C 1-6Alkyl, n is the integer of 0-5, recommends
Figure A20091004718200083
For
Figure A20091004718200084
R 3Be H, C 1-6The straight or branched alkyl, or have C 1-6The phenyl of alkyl substituent or halogen is recommended R 3For
Figure A20091004718200085
Wherein R ' is C 1～6Alkyl or halogen.→ be coordinate bond or do not have key; L is and rare earth metal coordinate solvent, as tetrahydrofuran (THF), and glycol dimethyl ether or ether etc., m is 0～5.X is and alkyl or the amido of rare earth ion Cheng Jian, and described alkyl or amido with rare earth ion Cheng Jian can be alkyl or the amido that replaces, and described substituting group can be a silylation etc.X can be the C with rare earth ion Cheng Jian 1-6Alkyl, [three (C 1～C 30Alkyl)] C of silica-based replacement 1-6Alkyl, two (C 1-8Alkyl) amido or two [three (C 1-8Alkyl) silica-based] amido.Described and alkyl or amido (X) rare earth ion Cheng Jian are recommended as C 1～C 30, further be recommended as C 1～C 10, as CH 2Si (CH 3) 3Or N (Si (CH 3) 3) 2
RE is a rare earth metal.Described rare earth metal is recommended as Y, Sc and all lanthanide series metals, further is recommended as Sc, Y, Lu, Gd, Dy or Nd.
Figure A20091004718200086
Expression delocalized conjugated double bond.
Above-mentioned novel three-tooth nitrogen ligand of the present invention can be directly be made by corresponding single imines and corresponding diamine reaction, also can make yield 40-90% through twice condensation with different amine by corresponding beta diketone.Specifically make by following reaction (2) or reaction (1), (2):
(1) by structural formula is
Figure A20091004718200091
Beta diketone and arylamine
Figure A20091004718200092
In mol ratio is 1: 0.2～3 o'clock, and in the presence of 0.1%～3% molar equivalent tosic acid, in organic solvents such as toluene, benzene, methyl alcohol or ethanol, reaction made intermediate list imines in 1～100 hour under 0 ℃～110 ℃
Figure A20091004718200093
(2) then in organic solvents such as toluene, benzene, methylene dichloride, triethylamine, methyl alcohol or ethanol, single imines of above-mentioned (1) and 0.2～3 normal diamines In the presence of 0.05%～3% molar equivalent vitriol oil or tosic acid or at 1～5 molar equivalent BF 4OEt 3Exist down, reaction made described novel three-tooth nitrogen ligand in 1～100 hour under 0 ℃～150 ℃.The vitriolic weight percent is 70%～98.3% in the described vitriol oil recommendation sulphuric acid soln.
R wherein 1Be C 1-10Alkyl; R 2Be H, C 1-6Alkyl or halogen, n is the integer of 0-5; R 3Be H, C 1-6The straight or branched alkyl, or have C 1-6The phenyl of alkyl substituent or halogen.
Rare earth metal complex of the present invention can be made by above-mentioned part and rare earth metal alkyl or amino-complex reaction; Perhaps part by after KH, NaH or the lithium alkylide deprotonation with RECl 3After reaction obtains corresponding rare-earth metal chloride, make with the MX reaction, yield is 50～90% again.Specifically, can finish by following reaction:
By above-mentioned part with generated in-situ or separate the REX that obtains 3(L) mIn organic solvents such as hexane, toluene, benzene, ether or tetrahydrofuran (THF), reaction made in 0.1～20 hour under-30 ℃～100 ℃.
Wherein X is-CH 2Si (CH 3) 3Or-N (Si (CH 3) 3) 2L is and rare earth metal coordinate solvent, as tetrahydrofuran (THF), and glycol dimethyl ether or ether etc., m is 0～5.
After can also at first forming sylvite, sodium salt or lithium salts by above-mentioned part in addition, again with 0.2～3 normal RECl with KH, NaH or lithium alkylide deprotonation 3In organic solvents such as hexane, toluene, benzene, ether or tetrahydrofuran (THF), reaction made muriate in 0.1～20 hour under-30 ℃～100 ℃, and this muriate and 0.2～3 normal MX reaction obtain product then.
Wherein M is Li, Na, K; X is-CH 2Si (CH 3) 3Or-N (Si (CH 3) 3) 2
Described lithium alkylide is recommended LiCH 2SiMe 3Deng.
Synthetic novel nitrogen-containing rare earth metal complex of the present invention can be used as catalyzer, further recommends to be used for the polyreaction of catalysis hydroamination reaction and ester.For the catalysis hydroamination reaction, especially be recommended in the organic solvents such as benzene, toluene, hexane, tetrahydrofuran (THF) or methylene dichloride or under the solvent-free state catalysis hydroamination reaction efficiently under-20 ℃～100 ℃ conditions.For the polyreaction of catalysis ester, especially be recommended in the organic solvents such as toluene, tetrahydrofuran (THF), methylene dichloride or hexane or under the solvent-free state ring-opening polymerization of catalyzing lactone efficiently under-20 ℃～160 ℃ conditions.
Embodiment
The present invention will be helped further to understand by following embodiment, but content of the present invention can not be limited.
Embodiment 1
In the 250mL three-necked bottle, add 2-(2,6-diisopropyl benzene amido)-2-amylene-4-ketone (5.58,21.5mmol), the N-tertiary butyl-(1) (2.5g, 21.5mmol), the tosic acid and the 100mL toluene of catalytic amount.Reflux water-dividing is 24 hours under the protection of nitrogen gas.Finally obtain light yellow oily product three-tooth nitrogen ligand L13.4g (136 ℃/5Pa), productive rate 45%.With 1HNMR, 13C NMR and mass spectral characteristi the structure of part. 1H NMR (300MHz, C 6D 6, 25 ℃): δ (ppm) 11.03 (br, 1H, MeC (NH) CH), 7.06-7.18 (m, 3H, ArH), 4.67 (s, 1H, MeC (N) CH), 3.14 (sp, 3J HH=6.6Hz, 2H, ArCHMe 2), 2.97 (q, 2H, NCH 2), 2.45 (t, 3J HH=6.3Hz, 2H, NCH 2), 1.68 (s, 3H, MeC), 1.64 (s, 3H, MeC), 1.24 (d, 3J HH=6.9Hz, 6H, ArCHMe 2), 1.20 (d, 3J HH=6.9Hz, 6H, ArCHMe 2), 0.88 (s, 9H, NCMe 3), 0.45 (br, 1H, tBu-NH). 1H NMR (300MHz, CDCl 3, 25 ℃): δ (ppm) 10.83 (br, 1H, MeC (NH) CH), 6.99-7.12 (m, 3H, ArH), 4.65 (s, 1H, MeC (N) CH), 3.34 (br, 2H, NCH 2), 2.87 (sp, 2H, ArCHMe 2), 2.68 (br, 2H, NCH 2), 2.02 (s, 3H, MeC), 1.62 (s, 3H, MeC), 1.17 (d, 3J HH=6.9Hz, 6H, ArCHMe 2), 1.13 (d, 3J HH=6.9Hz, 6H, ArCHMe 2), 1.03 (s, 9H, CMe 3), 0.82 (br, 1H, tBu-NH). 13C NMR (75MHz, CDCl 3, 25 ℃): δ (ppm) 165.8,155.5 (imine C), 146.6,137.7,122.4,122.3 (ArC), 93.1 (MeC (N) CH), 49.9,44.2,43.1 (NCH 2And NCMe 3), 28.8,27.8,23.6,22.6,21.4,19.4 (Ar iPr, MeC and NCMe 3) .HRMS (EI) C 23H 39N 3(M +) calculated value 357.3144; Measured value 357.3145.
Embodiment 2
In the 250mL three-necked bottle, add 2-(2,6-diisopropyl benzene amido)-2-amylene-4-ketone (14.6g, 56.3mmol), N-2,6-3,5-dimethylphenyl-(1) (9.5g, 57.8mmol), the tosic acid and the 100mL toluene of catalytic amount.Reflux water-dividing is 24 hours under the protection of nitrogen gas.Reaction finishes final vacuum except that desolvating, and gets brown thick substances.Recrystallizing methanol gets white solid three-tooth nitrogen ligand L212g, productive rate 52%.With 1H NMR, 13C NMR and mass spectral characteristi the structure of part. 1H NMR (300MHz, C 6D 6, 25 ℃): δ (ppm) 11.18 (br, 1H, MeC (NN) CH), 7.13-7.22 (m, 3H, ArH), 6.87-6.96 (m, 3H, ArH), 4.71 (s, 1H, MeC (NH) CH), 3.17 (sp, 3J HH=7.2Hz, 2H, ArCHMe 2), 3.15 (br, 1H, NH), 2.92 (br, 2H, NCH 2), 2.86 (br, 2H, NCH 2), 2.14 (s, 6H, ArMe), 1.67 (s, 3H, MeC), 1.58 (s, 3H, MeC), 1.22 (d, 3J HH=6.9Hz, 6H, ArCHMe 2), 1.21 (d, 3J HH=6.9Hz, 6H, ArCHMe 2). 1H NMR (300MHz, CDCl 3, 25 ℃): δ (ppm) 10.99 (br, 1H, MeC (NH) CH), 7.00-7.12 (m, 3H, ArH), 6.97 (d, 3J HH=7.2Hz, 2H, ArH 3 or 5), 6.81 (t, 3J HH=7.5Hz, 1H, ArH 4), 4.69 (s, 1H, MeC (N) CH), 3.37 (br, 2H, NCH 2), 3.27 (br, 1H, NH), 3.12 (br, 2H, NCH 2), 2.89 (sp, 3J HH=6.9Hz, 2H, ArCHMe 2), 2.22 (s, 6H, ArMe), 1.94 (s, 3H, MeC), 1.65 (s, 3H, MeC), 1.16 (d, 3J HH=6.9Hz, 6H, ArCHMe 2), 1.10 (d, 3J HH=6.9Hz, 6H, ArCHMe 2). 13C NMR (75MHz, CDCl 3, 25 ℃): δ (ppm) 166.3,155.8 (imine C), 146.6,145.2,138.0,129.5,128.8,122.7,122.6,121.9 (ArC), 93.7 (MeC (N) CH), 48.6,43.5 (NCH 2), 28.0,23.8,22.8,21.7,19.4,18.3 (ArMe, Ar iPr and MeC) .HRMS (EI) C 27H 39N 3(M +) calculated value 405.3144; Measured value 405.3146.
Embodiment 3
In the 250mL three-necked bottle, add 2-(2,6-diisopropyl benzene amido)-2-amylene-4-ketone (7.06g, 27.2mmol), N-2,6-diisopropyl phenyl-(1) (6g, 27.2mmol), the tosic acid and the 100mL toluene of catalytic amount.Reflux water-dividing is 24 hours under the protection of nitrogen gas.Reaction finishes final vacuum except that desolvating, and gets brown thick substances.Recrystallizing methanol gets white solid three-tooth nitrogen ligand L35.5g, productive rate 44%.With 1HNMR, 13CNMR and mass spectral characteristi the structure of part. 1HNMR (300MHz, C 6D 6, 25 ℃): δ (ppm) 11.29 (br, s, 1H, MeC (NH) CH), 7.24-7.25 (br, m, 6H, ArH), 4.80 (s, 1H, MeC (NH) CH), 3.36 (sp, 3J HH=7.2Hz, 2H, ArCHMe 2), 3.23 (sp, 3J HH=6.9Hz, 2H, ArCHMe 2), 3.15 (br, 2H, NCH 2), 2.98 (br, 2H, NCH 2), 1.75 (s, 3H, MeC), 1.74 (s, 3H, MeC), 1.29 (d, 3J HH=7.2Hz, 12H, ArCHMe 2), 1.25 (d, 3J HH=6.9Hz, 12H, ArCHMe 2). 1H NMR (300MHz, CDCl 3, 25 ℃): δ (ppm) 10.99 (br, 1H, MeC (NH) CH), 7.01-7.11 (m, 6H, ArH), 4.70 (s, 1H, MeC (N) CH), 3.46 (br, 2H, NCH 2), 3.20 (sp, 3J HH=6.6Hz, 2H, ArCHMe 2), 3.06 (br, 1H, NH), 3.00 (br, 2H, NCH 2), 2.87 (sp, 3J HH=6.6Hz, 2H, ArCHMe 2), 2.04 (s, 3H, MeC), 1.65 (s, 3H, MeC), 1.14-1.18 (m, 18H, ArCHMe 2), 1.09 (d, 3J HH=6.6Hz, 6H, ArCHMe 2). 13C NMR (75MHz, CDCl 3, 25 ℃): δ (ppm) 166.2,155.6 (imine C), 146.6,142.6,142.5,137.9,123.9,123.5,122.7,122.6 (ArC), 93.7 (MeC (N) CH), 52.1,43.8 (NCH 2), 28.1,28.0,27.6,24.2,23.7,22.8,21.6,19.3 (Ar iPr and MeC) .HRMS (EI) C 31H 47N 3(M +) calculated value 461.3770; Measured value 461.3768.
Embodiment 4
In exsiccant 50mL Schlenk pipe, nitrogen protection adds BF down 4OEt 3(0.997g is 5.25mmol) with 10mL exsiccant methylene dichloride.Under the room temperature, in above-mentioned solution, add 2-(2,6-diisopropyl benzene amido)-2-amylene-4-ketone (1.5g, 5.78mmol).Stirring at room 3 hours.Add the 1.5mL triethylamine subsequently in above-mentioned mixed solution, stirring at room is after 15 minutes, again to the triethylamine solution that wherein adds anhydrous ethylenediamine (0.315g quadrol, 8mL triethylamine).Finished stirring at room 24 hours.Solvent removed in vacuo, crude product extracts with toluene, filters the filtrate solvent removed in vacuo.Gained oily matter gets colourless crystallization solid three-tooth nitrogen ligand L40.9g, productive rate 52% with recrystallizing methanol.With 1H NMR, 13C NMR has characterized the structure of part. 1H NMR (300MHz, C 6D 6, 25 ℃): δ (ppm) 10.93 (br, s, 1H, MeC (NH) CH), 7.09-7.12 (m, 2H, ArH), 7.00-7.04 (m, 1H, ArH), 4.64 (s, 1H, MeC (NH) CH), 3.30 (s, 2H, CH 2NH 2), 2.84 (sp, 3J HH=6.9Hz, 2H, ArCHMe 2), 1.96 (s, 3H, MeC), 1.62 (s, 3H, MeC), 1.14 (d, 3J HH=7.2Hz, 6H, ArCHMe 2), 1.10 (d, 3J HH=6.9Hz, 6H, ArCHMe 2). 13C NMR (75MHz, CDCl 3, 25 ℃): δ (ppm) 166.2,155.3 (imine C), 146.6,138.0,122.7,122.6 (ArC), 93.7 (MeC (N) CH), 44.4 (NCH 2), 28.0,23.8,22.7,21.6,19.1 (Ar iPr and MeC).
Embodiment 5
With 5.11g 2-(2,6-diisopropyl benzene amido)-2-amylene-4-ketone, 4.12g N-(2, the 6-dichlorophenyl) tosic acid of quadrol and catalytic amount is dissolved in 80ml toluene, reflux is divided water reaction 20h, solvent removed in vacuo toluene, anhydrous methanol recrystallization get 4.51g white powder three-tooth nitrogen ligand L5, productive rate 51%.With 1H NMR, 13C NMR and mass spectral characteristi the structure of part. 1H NMR (300MHz, CDCl 3, 25 ℃): δ (ppm) 11.02 (br, 1H, MeC (NH) CH), 7.21 (d, 3J HH=7.8Hz, 2H, ArH), 7.11-7.00 (m, 3H, ArH), 6.78 (t, 3J HH=7.8Hz, 1H, ArH), 4.69 (s, 1H, MeC (NH) CH), 4.19 (br, 1H, NH), 3.43 (br, 2H, NCH 2), 3.42 (br, 2H, NCH 2), 2.89 (sp, 3J HH=6.9Hz, 2H, ArCHMe 2), 1.99 (s, 3H, MeC), 1.64 (s, 3H, MeC), 1.16 (d, 3J HH=6.9Hz, 6H, ArCHMe 2), 1.10 (d, 3J HH=6.9Hz, 6H, ArCHMe 2). 13C NMR (75MHz, CDCl 3, 25 ℃): δ (ppm) 166.0,155.7 (imine C), 146.4,142.2,138.1,128.7,126.5,123.0,122.7,122.0 (ArC), 93.9 (MeC (N) CH), 48.0,43.6 (NCH 2), 28.0,23.8,22.8,21.6,19.4 (Ar iPr and MeC) .HRMS (EI) C 25H 33Cl 2N 3(M +) calculated value 445.2052; Measured value 445.2055.
Embodiment 6
With 3.03g 2-(2,6-dichlorobenzene amido)-2-amylene-4-ketone, the tosic acid of 2.04gN-(2, the 6-3,5-dimethylphenyl) quadrol and catalytic amount is dissolved in 70ml toluene, and reflux is divided water reaction 20h, and solvent removed in vacuo toluene obtains the oily crude product.The column chromatography separation obtains 2.96g yellow oily three-tooth nitrogen ligand L6, productive rate 61%.With 1H NMR and 13C NMR has characterized the structure of part. 1H NMR (300MHz, CDCl 3, 25 ℃): δ (ppm) 10.71 (br, 1H, MeC (NH) CH), 7.28 (d, 3J HH=8.0Hz, 2H, ArH), 6.95 (d, 3J HH=7.6Hz, 2H, ArH), 6.86 (t, 3J HH=8.0Hz, 1H, ArH), 6.80 (t, 3J HH=7.6Hz, 1H, ArH), 4.75 (s, 1H, MeC (NH) CH), 3.43 (q, 3J HH=5.6Hz, 2H, NCH 2), 3.30-3.38 (br, 1H, NH), 3.15 (t, 3J HH=5.6Hz, 2H, NCH 2), 2.21 (s, 6H, ArMe), 1.96 (s, 3H, MeC), 1.75 (s, 3H, MeC). 13C NMR (100MHz, CDCl 3, 25 ℃): δ (ppm) 168.7,157.6 (imine C), 146.4,145.0,129.8,128.7,127.8,127.1,122.8,122.0 (ArC), 93.6 (MeC (N) CH), 48.1,43.5 (NCH 2), 22.0,19.5,18.2 (ArMe and MeC).
Embodiment 7
With L2 (260mg, 0.641mmol) and Sc (CH 2SiMe 3) 3(THF) 2(288mg 0.642mmol) respectively is dissolved in the 5mL hexane.After-36 ℃ of cooling half an hour, the hexane solution of L2 is once joined Sc (CH 2SiMe 3) 3(THF) 2Hexane solution in.Reaction solution is that light yellow summary is transparent redly.Behind the room temperature reaction 1 hour, solvent removed in vacuo gets light yellow solid.Behind the hexane recrystallization, obtain white crystalline solid L2Sc (CH 2SiMe 3) (THF) (7) (276mg, productive rate 71%).With 1H NMR, 13C NMR, ultimate analysis and fusing point have characterized its structure.Fusing point 76-78 ℃.C 35H 55N 3The ultimate analysis data of OSiSc: calculated value: C, 69.27; H, 9.13; N, 6.92. measured value: C, 69.29; H, 9.07; N, 7.05. 1H NMR (300MHz, C 6D 6, 25 ℃): δ (ppm) 7.12 (d, 3J HH=7.2Hz, 1H, ArH 3 or 5), 7.03-6.96 (m, 4H, ArH), 6.85 (t, 3J HH=7.6Hz, 1H, ArH 4), 5.05 (s, 1H, MeC (N) CH), 4.24 (m, 1H, THF-H α), 4.04 (m, 1H, THF-H α), 3.64-3.55 (m, 2H, THF-H αAnd ArCHMe 2), 3.21-3.12 (m, 3H, NCH 2And ArCHMe 2), 3.06 (m, 1H, THF-H α), 2.72 (s, 3H, ArMe), 2.58 (br, 2H, NCH 2), 2.32 (s, 3H, ArMe), 1.91 (s, 3H, MeC), 1.63 (s, 3H, MeC), 1.25 (d, 3J HH=6.9Hz, 3H, ArCHMe 2), 1.17 (d, 3J HH=6.9Hz, 3H, ArCHMe 2), 1.13 (d, 3J HH=6.9Hz, 3H, ArCHMe 2), 1.01 (d, 3J HH=6.6Hz, 3H, ArCHMe 2), 0.67 (br, 2H, THF-H β), 0.58 (br, 2H, THF-H β), 0.42 (s, 9H, CH 2SiMe 3), 0.19 (d, 2J HH=11.1Hz, 1H, CH 2SiMe 3) ,-0.42 (d, 2J HH=11.1Hz, 1H, CH 2SiMe 3). 13C NMR (75MHz, C 6D 6, 25 ℃): δ (ppm) 166.1,164.8 (imine C), 157.9,147.0,145.7,143.7,136.0,134.0,126.2,125.0,124.2,122.4 (ArC), 99.7 (MeC (N) CH), 71.0 (THF-C α), 56.9,54.7 (NCH 2), 32.6 (CH 2SiMe 3), 29.3,28.0,25.9,25.6,25.3,25.2,25.1,24.9,22.6,21.0,20.5 (ArMe, Ar iPr, THF-C βAnd MeC), 4.7 (CH 2SiMe 3).
Embodiment 8
With L2 (228.4mg, 0.563mmol) and Y (CH 2SiMe 3) 3(THF) 2(277.5mg 0.563mmol) respectively is dissolved in the 5mL hexane.After-36 ℃ of cooling half an hour, the hexane solution of L2 is once joined Y (CH 2SiMe 3) 3(THF) 2Hexane solution in.Reaction solution is that light yellow summary is transparent redly.Behind the room temperature reaction 1 hour, solvent removed in vacuo gets light yellow solid.Behind the hexane recrystallization, obtain light yellow crystalline solid L2Y (CH 2SiMe 3) (THF) (8) (275.2mg, productive rate 75%).With X-Ray, 1H NMR, 13C NMR, ultimate analysis and fusing point have characterized its structure.Fusing point 118-120 ℃.C 35H 55N 3The ultimate analysis data of OSiY: calculated value: C, 64.59; H, 8.52; N, 6.46. measured value: C, 64.17; H, 8.02; N, 6.22. 1H NMR (300MHz, C 6D 6, 25 ℃): δ (ppm) 7.08 (d, 3J HH=7.5Hz, 2H, ArH 3 or 5), 6.99-6.94 (m, 3H, ArH), 6.83 (t, 3J HH=7.3Hz, 1H, ArH 4), 5.00 (s, 1H, MeC (N) CH), 4.24 (m, 2H, THF-H α), 3.63-3.55 (m, 2H, THF-H αAnd ArCHMe 2), 3.16-3.08 (m, 2H, THF-H αAnd ArCHMe 2), 2.95 (q, 2H, NCH 2), 2.54 (br, 6H, ArMe), 2.43 (q, 2H, NCH 2), 1.92 (s, 3H, MeC), 1.64 (s, 3H, MeC), 1.23 (d, 3J HH=6.9Hz, 3H, ArCHMe 2), 1.16 (d, 3J HH=6.9Hz, 3H, ArCHMe 2), 1.14 (d, 3J HH=6.9Hz, 3H, ArCHMe 2), 1.03 (d, 3J HH=6.9Hz, 3H, ArCHMe 2), 0.73 (m, 2H, THF-H β), 0.65 (m, 2H, THF-H β), 0.45 (s, 9H, CH 2SiMe 3) ,-0.21 (dd, 2J HH=10.8Hz, 2J YH=3.3Hz, 1H, CH 2SiMe 3) ,-0.66 (dd, 2J HH=10.8Hz, 2J YH=3.3Hz, 1H, CH 2SiMe 3). 13C NMR (75MHz, C 6D 6, 25 ℃): δ (ppm) 166.3,162.6 (imine C), 156.9,145.1,144.0,143.8,134.1,125.4,124.2,123.9,120.7 (ArC), 98.5 (MeC (N) CH), 69.4 (THF-C α), 56.7,55.5 (NCH 2), 32.1 (d, 1J YC=45.9Hz, CH 2SiMe 3), 28.2,27.8,25.4,25.1,24.5,23.9,23.8,22.4,20.6 (ArMe, Ar iPr, THF-C βAnd MeC), 4.3 (CH 2SiMe 3).
Embodiment 9
With L2 (104mg, 0.258mmol) and Lu (CH 2SiMe 3) 3(THF) 2(150mg 0.258mmol) respectively is dissolved in the 5mL hexane.After-36 ℃ of cooling half an hour, the hexane solution of L2 is once joined Lu (CH 2SiMe 3) 3(THF) 2Hexane solution in.Reaction solution is that light yellow summary is transparent redly.Behind the room temperature reaction 1 hour, solvent removed in vacuo gets light yellow solid.Behind the hexane recrystallization, obtain white crystalline solid L2Lu (CH 2SiMe 3) (THF) (9) (175mg, productive rate 90%).With 1H NMR, 13C NMR, ultimate analysis and fusing point have characterized its structure.Fusing point 125-127 ℃.C 35H 55N 3The ultimate analysis data of OSiLu: calculated value: C, 57.05; H, 7.52; N, 5.70. measured value: C, 56.58; H, 6.75; N, 5.65. 1H NMR (300MHz, C 6D 6, 25 ℃): δ (ppm) 7.08 (br, 2H, ArH 3 or 5), 6.98 (m, 3H, ArH), 6.83 (t, 3J HH=7.2Hz, 1H, ArH 4), 4.98 (s, 1H, MeC (N) CH), 4.15 (m, 2H, THF-H α), 3.63-3.55 (m, 2H, THF-H αAnd ArCHMe 2), 3.22-3.14 (m, 2H, THF-H αAnd ArCHMe 2), 3.00 (q, 2H, NCH 2), 2.57 (br, 6H, ArMe), 2.45 (q, 2H, NCH 2), 1.89 (s, 3H, MeC), 1.63 (s, 3H, MeC), 1.24 (d, 3J HH=6.6Hz, 3H, ArCHMe 2), 1.18 (d, 3J HH=6.9Hz, 3H, ArCHMe 2), 1.16 (d, 3J HH=6.9Hz, 3H, ArCHMe 2), 1.04 (d, 3J HH=6.6Hz, 3H, ArCHMe 2), 0.72 (m, 2H, THF-H β), 0.59 (m, 2H, THF-H β), 0.46 (s, 9H, CH 2SiMe 3) ,-0.36 (d, 2J HH=11.1Hz, 1H, CH 2SiMe 3) ,-0.80 (d, 2J HH=11.1Hz, 1H, CH 2SiMe 3). 13C NMR (75MHz, C 6D 6, 25 ℃): δ (ppm) 166.7,163.7 (imine C), 157.9,145.0,144.9,143.6,125.4,124.2,123.9,120.9 (ArC), 99.0 (MeC (N) CH), 69.8 (THF-C α), 56.4,55.0 (NCH 2), 38.0 (CH 2SiMe 3), 28.4,27.6,25.3,25.0,24.8,24.4,24.3,24.1,22.3,20.5 (ArMe, Ar iPr, THF-C βAnd MeC), 4.4 (CH 2SiMe 3).
Embodiment 10
With L3 (142mg, 0.306mmol) and Y (CH 2SiMe 3) 3(THF) 2(150mg 0.305mmol) respectively is dissolved in the 5mL hexane.After-36 ℃ of cooling half an hour, the hexane solution of L3 is once joined Y (CH 2SiMe 3) 3(THF) 2Hexane solution in.Behind the room temperature reaction 1 hour, solvent removed in vacuo gets white solid.Behind the hexane recrystallization, obtain white crystalline solid L3Y (CH 2SiMe 3) (THF) (10) (127mg, productive rate 59%).With 1H NMR, 13C NMR, ultimate analysis and fusing point have characterized its structure.Fusing point 148-150 ℃.C 39H 63N 3The ultimate analysis data of OSiY: calculated value: C, 66.26; H, 8.98; N, 5.94. measured value: C, 66.15; H, 9.22; N, 5.59. 1H NMR (300MHz, C 6D 6, 25 ℃): δ (ppm) 7.23 (t, 3J HH=4.8Hz, 1H, ArH 4), 7.06 (d, 3J HH=4.5Hz, 2H, ArH 3 or 5), 6.96 (m, 3H, ArH), 5.03 (s, 1H, MeC (N) CH), 4.79 (sp, 3J HH=6.6Hz, 1H, ArCHMe 2), 4.38 (m, 2H, THF-H α), 3.67-2.57 (m, 3H, THF-H αAnd ArCHMe 2), 3.12-2.99 (m, 4H, THF-H α, ArCHMe 2And N-CH 2), 2.40 (q, 2H, NCH 2), 1.94 (s, 3H, MeC), 1.61 (s, 3H, MeC), 1.55 (d, 3J HH=7.2Hz, 3H, ArCHMe 2), 1.40 (d, 3J HH=6.6Hz, 3H, ArCHMe 2), 1.39 (d, 3J HH=6.6Hz, 3H, ArCHMe 2), 1.25 (d, 3J HH=6.9Hz, 3H, ArCHMe 2), 1.19 (d, 3J HH=6.9Hz, 3H, ArCHMe 2), 1.16 (d, 3J HH=6.6Hz, 3H, ArCHMe 2), 1.06 (d, 3J HH=6.9Hz, 3H, ArCHMe 2), 1.04 (d, 3J HH=6.9Hz, 3H, ArCHMe 2), 0.77 (m, 2H, THF-H β), 0.64 (m, 2H, THF-H β), 0.46 (s, 9H, CH 2SiMe 3) ,-0.13 (dd, 2J HH=10.8Hz, 2J YH=3.3Hz, 1H, CH 2SiMe 3) ,-0.68 (dd, 2J HH=10.8Hz, 2J YH=3.3Hz, 1H, CH 2SiMe 3), 13C NMR (75MHz, C 6D 6, 25 ℃): δ (ppm) 167.1,163.3 (imine C), 155.8,146.7,145.9,145.8,144.6,144.5,126.2,124.9,124.6,124.1,123.7,122.9 (ArC), 99.3 (MeC (N) CH), 70.2 (THF-C α), 61.0,56.4 (NCH 2), 32.5 (d, 1J YC=47.4Hz, CH 2SiMe 3), 28.9,28.6,28.5,28.4,28.0,26.2,25.9,25.8,25.3,24.7,24.4,24.1,23.5,23.2 (Ar iPr, THF-C βAnd MeC), 4.8 (CH 2SiMe 3).
Embodiment 11
50mL cock bottle adds anhydrous DyCl 3(225mg, 0.837mmol), 10mL THF, stirred overnight at room temperature.Solvent removed in vacuo adds the 5mL normal hexane, and stirring at room 1 hour gets grey suspension.Under the room temperature, to wherein dripping LiCH 2SiMe 3Hexane solution (232mg, 2.47mmol are dissolved in the 5mL normal hexane).Drip and finish, stirring at room 1 hour generates grey viscosity insolubles.Centrifugal, supernatant liquid is added drop-wise under 0 ℃ in the hexane solution of L3 (318mg, 0.689mmol are dissolved in the 10mL normal hexane).Drip and finish, 0 ℃ was stirred 2 hours, and rose to room temperature naturally.Centrifugal, shift supernatant liquid, concentrate ,-36 ℃ are freezing, obtain white crystalline solid L3Dy (CH 2SiMe 3) (THF) (11) 485mg, productive rate 90%.Characterized its structure with ultimate analysis and fusing point.Fusing point 149-151 ℃.C 39H 63N 3The ultimate analysis calculated value of OSiDy: C, 60.01; H, 8.14; N, 5.38. measured value: C, 60.20; H, 8.07; N, this complex compound of 5.21. is a paramagnetic compound.
Embodiment 12
50mL cock bottle adds anhydrous GdCl 3(187mg, 0.709mmol), 10mL THF, stirred overnight at room temperature.Solvent removed in vacuo adds the 5mL normal hexane, and stirring at room 1 hour gets grey suspension.Under the room temperature, to wherein dripping LiCH 2SiMe 3Hexane solution (197mg, 2.09mmol are dissolved in the 5mL normal hexane).Drip and finish, stirring at room 1 hour generates grey viscosity insolubles.Centrifugal, supernatant liquid is added drop-wise under 0 ℃ in the hexane solution of L3 (278mg, 0.602mmol are dissolved in the 10mL normal hexane).Drip and finish, 0 ℃ was stirred 2 hours, and rose to room temperature naturally.Centrifugal, shift supernatant liquid, concentrate ,-36 ℃ are freezing, obtain white crystalline solid L3Gd (CH 2SiMe 3) (THF) (12) 251mg, productive rate 54%.Characterized its structure with ultimate analysis and fusing point.Fusing point 131-133 ℃.C 39H 63N 3The ultimate analysis calculated value of OSiGd: C, 60.42; H, 8.19; N, 5.42. measured value: C, 61.48; H, 8.72; N, this complex compound of 5.18. is a paramagnetic compound.
Embodiment 13
50mL cock bottle adds anhydrous NdCl 3(230mg, 0.918mmol), 10mL THF, stirring is spent the night.Under the ice-water bath, drip LiCH 2SiMe 3THF solution (254.9mg, 2.708mmol in 10mL THF) in NdCl 3In.Drip and finish, rose to stirring at room naturally 2 hours, solution generates viscosity grey insolubles simultaneously by the colourless sky blue that becomes.After 2 hours, be cooled to 0 ℃, drip the THF solution (360.3mg, 0.78mmol are dissolved in 5mL THF) of L3.Drip and finish, solution colour becomes blue-greenish colour by sky blue.0 ℃ was stirred solvent removed in vacuo 2 hours.Add the 5mL normal hexane, drain once more, gained solid 10mL n-hexane extraction, centrifugal, migrate out upper strata blue-greenish colour clear liquid, concentrate-36 ℃ of frozen recrystallizations.Obtain green crystal L3Nd (CH 2SiMe 3) (THF) (13) 393mg, productive rate 78%.Characterized its structure with X-Ray, ultimate analysis and fusing point.Fusing point 137-139 ℃.C 39H 63N 3The ultimate analysis calculated value of OSiNd: C, 61.45; H, 8.33; N, 5.51. measured value: C, 61.30; H, 8.88; N, 5.22.This complex compound is a paramagnetic substance.
Embodiment 14
With L3 (243mg, 0.526mmol) and Dy (N (SiMe 3) 2) 3(338mg 0.526mmol) respectively is dissolved in the 5mL hexane, after-36 ℃ of cooling half an hour, the hexane solution of L3 is once joined Dy (N (SiMe 3) 2) 3Hexane solution in.Reaction solution is light yellow transparent.60 ℃ of reactions are after 24 hours, and solvent removed in vacuo gets light yellow solid.Behind the hexane recrystallization, obtain white crystalline solid L3Dy (N (SiMe 3) 2) (14) 284mg, productive rate 69%.Characterized its structure with ultimate analysis and fusing point.Fusing point 140-142 ℃.C 37H 63N 4Si 2The ultimate analysis calculated value of Dy: C, 56.78; H, 8.11; N, 7.16. measured value: C, 56.22; H, 8.07; N, 7.21.This complex compound is a paramagnetic substance.
Embodiment 15
With rare earth catalyst L3Nd (CH 2SiMe 3) (THF) (13) (7.62mg, 10 μ mol) and 4,4-dimethyl-5-amido-1-amylene (200-500 equivalent) mixes and is dissolved in 0.5mL benzene.In 60 ℃ oil bath, react.Partial reaction the results are shown in Table 1.
Embodiment 16
With 0.44g rac-lactide and rare earth compounding L2Y (CH 2SiMe 3) mixing of (THF) (8) (10mg, 15 μ mol) solid, add the 3mL tetrahydrofuran (THF).Behind the room temperature reaction 40 minutes, with a wet tetrahydrofuran (THF) with its cancellation, rapid solvent removed in vacuo. 1The yield that HNMR records polylactide is 86%.Resulting polymers with 1It is 0.66 with selectivity that H calculates it assorted with nuclear decoupling NMR.
Embodiment 17
With 0.44 with 0.44g rac-lactide and rare earth compounding L2Y (CH 2SiMe 3) mixing of (THF) (8) (10mg, 15 μ mol) solid, add the 3mL methylene dichloride.Behind the room temperature reaction 40 minutes, with a wet tetrahydrofuran (THF) with its cancellation, rapid solvent removed in vacuo. 1The yield that H NMR records polylactide is 65%.Resulting polymers with 1It is 0.64 with selectivity that H calculates it assorted with nuclear decoupling NMR.
Part catalysis 4, the result such as the following table of 4-dimethyl-5-amido-1-amylene intramolecularly hydroamination reaction:
Table 1. rare earth metal complex is catalytic 4,4-dimethyl-5-amido-1-amylene intramolecularly hydroamination reaction
Figure A20091004718200191
The structure of ligand L 1-L6 described in the embodiment is as follows:
L1：R＝ tBu L6：R＝2，6-Me 2-C 6H 3
L2：R＝2，6-Me 2-C 6H 3
L3：R＝2，6- iPr 2-C 6H 3
L4：R＝H
L5：R＝2，6-Cl 2-C 6H 3
The structure of catalyzer 7-14 is as follows:
Figure A20091004718200201
14：R＝2，6- iPr 2-C 6H 3，RE＝Dy。

Claims (13)

1. a class three-tooth nitrogen ligand is characterized in that having following structural formula:
Figure A2009100471820002C1
In the said structure formula, R 1Be C 1-10Alkyl; R 2Be H, C 1-6Alkyl or halogen, n is 0～5; R 3Be H, C 1-6Alkyl, have C 1-6The phenyl of alkyl substituent or halogen.
2. the rare earth compounding of three-tooth nitrogen ligand as claimed in claim 1 is characterized in that having following structural formula:
Figure A2009100471820002C2
In the said structure formula, RE is a rare earth ion; R 1, R 2, n, R 3According to claim 1; X is the C with rare earth ion Cheng Jian 1-6Alkyl, [three (C 1～C 30Alkyl)] C of silica-based replacement 1-6Alkyl, two (C 1-8Alkyl) amido or two [three (C 1-8Alkyl) silica-based] amido;
Figure A2009100471820002C3
Expression delocalized conjugated double bond; → be coordinate bond or do not have key; L is and rare earth metal coordinate solvent that m is 0～5.
3. rare earth compounding as claimed in claim 2 is characterized in that described L is tetrahydrofuran (THF), glycol dimethyl ether or ether.
4. rare earth compounding as claimed in claim 2 is characterized in that having following structural formula:
Described RE, R 1, R 2, R 3, X, →, L and m be as described in the claim 2.
5. rare earth compounding as claimed in claim 4 is characterized in that described X is CH 2Si (CH 3) 3Or N[Si (CH 3) 3] 2
6. rare earth compounding as claimed in claim 2 is characterized in that described rare earth metal is Y, Sc or lanthanide series metal.
7. rare earth compounding as claimed in claim 2 is characterized in that described rare earth metal is Sc, Y, Lu, Gd, Dy or Nd.
8. as the preparation method of each described rare earth compounding in the claim 2 to 7, it is characterized in that in organic solvent, under-30 ℃～100 ℃, by part and rare earth alkyl compound or amino-complex REX 3(L) mReaction 0.1～20h makes, wherein part and REX 3Mol ratio be 1: 0.2～3; After perhaps part forms salt by KH, NaH or lithium alkylide deprotonation, again with the RECl of 0.2～3 molar equivalent 3In organic solvent, after-30 ℃～100 ℃ reaction 0.1～20h obtains muriate down, make with the MX reaction again, wherein part, RECl 3, MX and KH, NaH or lithium alkylide mol ratio be 1: (0.2～3): (0.2～3): (0.2～3);
Described part according to claim 1;
Wherein, RE, L, m, X are as described in the claim 2, and M is Li, Na or K.
9. the described preparation method of claim 8 is characterized in that described organic solvent is normal hexane, toluene, benzene, ether or tetrahydrofuran (THF).
10. preparation method as claimed in claim 8 is characterized in that described part is synthetic by following reaction (1) and (2) or (2) two kinds of steps:
(1) in organic solvent and under 0 ℃～110 ℃, is by structural formula
Figure A2009100471820003C1
Beta diketone and arylamine
Figure A2009100471820003C2
In mol ratio is 1: 0.2～3 o'clock, reacts 1～100h and make the monolateral substituted imine of intermediate in the presence of 0.1%-3% molar equivalent tosic acid
Figure A2009100471820003C3
(2) then in organic solvent, single imines of above-mentioned (1) and 0.2～3 normal diamines
Figure A2009100471820003C4
In the presence of 0.05%～3% molar equivalent vitriol oil or tosic acid or at 1～5 molar equivalent BF 4OEt 3Exist down, reaction made the three-tooth nitrogen ligand described in the claim 9 in 1～100 hour under 0 ℃～150 ℃;
R wherein 1, R 2, R 3, n according to claim 1.
11. the described preparation method of claim 10 is characterized in that described organic solvent is toluene, benzene, methylene dichloride, triethylamine, methyl alcohol or ethanol.
12. the purposes of the described rare earth compounding of claim 2 is characterized in that being used for the catalyzer of the ring-opening polymerization of the ring-opening polymerization of catalysis hydroamination reaction and lactone, the hydroamination reaction that is used for catalyzed alkene or catalysis rac-Lactide.
13. the purposes of the described rare earth compounding of claim 2, it is characterized in that in benzene, toluene, hexane, dichloromethane solution, or under the solvent-free state, catalyzed alkene hydroamination reaction or in toluene, tetrahydrofuran (THF), methylene dichloride, hexane solution or under the solvent-free state under-20 ℃～120 ℃ conditions, the ring-opening polymerization of catalyzing lactone under-20 ℃～160 ℃ conditions.
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CN104418768B (en) * 2013-08-20 2018-11-27 中国科学院上海有机化学研究所 A kind of bimetallic olefin polymerization catalysts
CN103464207A (en) * 2013-09-03 2013-12-25 安徽师范大学 Rare-earth complex catalyst, and preparation method, application and application method thereof
CN103464207B (en) * 2013-09-03 2015-08-12 安徽师范大学 A kind of catalyzed by rare-earth complex agent, its preparation method, purposes and application process
CN111548487A (en) * 2020-05-13 2020-08-18 广州大学 Porous organic polymer and preparation method and application thereof
CN111548487B (en) * 2020-05-13 2022-08-30 广州大学 Porous organic polymer and preparation method and application thereof
CN114106308A (en) * 2020-08-31 2022-03-01 中国石油化工股份有限公司 Catalyst composition and application thereof, polylactide and preparation method thereof
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