CN101812084A - Rare earth metal amine compound containing aromatic amine methylene pyrrole ligand, preparation method and application thereof - Google Patents
Rare earth metal amine compound containing aromatic amine methylene pyrrole ligand, preparation method and application thereof Download PDFInfo
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- CN101812084A CN101812084A CN201010140266A CN201010140266A CN101812084A CN 101812084 A CN101812084 A CN 101812084A CN 201010140266 A CN201010140266 A CN 201010140266A CN 201010140266 A CN201010140266 A CN 201010140266A CN 101812084 A CN101812084 A CN 101812084A
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- rare earth
- earth metal
- toluene
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- -1 Rare earth metal amine compound Chemical class 0.000 title claims abstract description 36
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 30
- 239000003446 ligand Substances 0.000 title claims abstract description 18
- 150000004982 aromatic amines Chemical class 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- CQAOCWVRDYSQRD-UHFFFAOYSA-N 5-azabicyclo[3.1.0]hexa-1,3-diene Chemical compound C1=CN2CC2=C1 CQAOCWVRDYSQRD-UHFFFAOYSA-N 0.000 title abstract 2
- 125000003118 aryl group Chemical group 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 9
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 8
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 8
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 188
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 129
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000006555 catalytic reaction Methods 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 17
- 229910006400 μ-Cl Inorganic materials 0.000 claims description 15
- QTXIRQLISWYFOQ-UHFFFAOYSA-N NC=1C(N=CC=1)=C Chemical compound NC=1C(N=CC=1)=C QTXIRQLISWYFOQ-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001718 carbodiimides Chemical class 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 8
- 150000002910 rare earth metals Chemical class 0.000 claims description 8
- 229920002521 macromolecule Polymers 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000007259 addition reaction Methods 0.000 claims description 5
- QLSWIGRIBOSFMV-UHFFFAOYSA-N 1h-pyrrol-2-amine Chemical compound NC1=CC=CN1 QLSWIGRIBOSFMV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract 3
- 239000010703 silicon Substances 0.000 abstract 3
- 239000003054 catalyst Substances 0.000 abstract 1
- 125000003107 substituted aryl group Chemical group 0.000 abstract 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 63
- 239000000243 solution Substances 0.000 description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000002904 solvent Substances 0.000 description 16
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 13
- 238000000921 elemental analysis Methods 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 11
- 230000009466 transformation Effects 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 9
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 8
- 230000037048 polymerization activity Effects 0.000 description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 125000002524 organometallic group Chemical group 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000011343 solid material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000008431 aliphatic amides Chemical class 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 150000002357 guanidines Chemical class 0.000 description 2
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ZSKGQVFRTSEPJT-UHFFFAOYSA-N pyrrole-2-carboxaldehyde Chemical compound O=CC1=CC=CN1 ZSKGQVFRTSEPJT-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 241001148659 Panicum dichotomiflorum Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000003808 methanol extraction Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a rare earth metal amine compound containing aromatic amine methylene pyrrole ligand, a preparation method and application thereof. The structure of the amine compound has the following formula, wherein Ln is yttrium and lanthanide series metal; R1, R2 and R3 are H, C1 to C4 are linear chain or branched chain alkyls; R4 and R5 are H, or C1 to C4 are linear chain or branched chain alkyls or aryls; R6 is C1 to C4 linear chain or branched chain alkyl silicon bases, or aryl silicon bases, or substituted aryl silicon bases, or C1 to C4 linear chain or branched alkyls, or aryl or substituted aryl. Compared with the prior art, the invention has the characteristics of simple process and high catalytic activity of prepared catalysts.
Description
Technical field
The present invention relates to rare earth metal aminate catalyzer, preparation method and application thereof, exactly is that a class contains aromatic amino methylene pyrrole ligand rare earth metal aminate, preparation method and application thereof.
Background technology
Between the nearest more than ten years, containing the pyrryl rare earth metal complex is just becoming the focus that the Organometallic scholars study after the rare earth metallocene complex.The same with the rare earth metallocene complex, contain the pyrryl rare earth metal complex also need not promotor just can catalysis in olefine polymerization and the ring-opening polymerization of cyclic lactone.Outside the monomeric polymerization of decapacitation catalysis, contain the pyrryl rare earth metal complex efficiently the addition reaction of Atom economy ground catalysis amine and carbodiimide generate the guanidine compound of biologically active.
The polyester macromolecule that the polymerization of esters monomer (6-caprolactone and rac-Lactide) generates has been widely used in packing, weaving and bio-medical material owing to have characteristics such as favorable biological degradability, biocompatibility, nontoxic and workability.Studies show that in a large number the main group metal title complex add alcohols as initiator effectively the living polymerization of catalysis esters monomer generate polymkeric substance (T.M.Ovitt, G.W.Coates, J.Am.Chem.Soc.2002,124,1316 of narrow molecular weight distribution; H.Du, X.Pang, H.Yu, X, Zhuang, X.Chen, D.Cui, X.Wang, X.Jing, Macromolecules 2007,40, and 1904; H.-Y.Tang, H.-Y.Chen, J.-H.Huang, C.-C.Lin, Macromolecules 2007,40, and 8855).
J.Okuda etc. also reported the polymerization that OSSO type sulfur-bearing bridging biphenol group of the lanthanides aminate can efficient catalytic rac-rac-Lactide (Macromolecules 2005,38 for H.Y.Ma, J.Okuda, 2665; H.Y.Ma, T.P.Spaniol, J.Okuda, Inorg.Chem.2008,47,3328).Complex structure is as follows:
People such as Shen Qi have reported that also bridging amidino groups rare earth metal alkoxyl group and aryloxy title complex can cause the polymerization of L-rac-Lactide and 6-caprolactone (J.F.Wang, Y.M.Yao, Y.Zhang, Q.Shen, Inorg.Chem.2009,48,744).Complex structure is as follows:
Cui Dongmei etc. have synthesized series and have contained pyrryl rare earth metal silylation and amido title complex.These compounds can catalysis rac-LA the molecular weight distribution that obtains of polymerization (Y.Yang, S.Li, D.Cui, X.Chen, X.Jing, Organometallics 2007,26,671) between 1.12～1.75.Complex structure is as follows:
Guanidine compound has application widely because it has physiologically active at field of medicaments, and many guanidine compounds can be used as drug use.The method of traditional synthetic guanidine compound is synthetic by amine (ammonia) and guanidine radicals reagent effects such as nitrile amine, lsothiocyanates and isothiourea, amido imide methylsulfonic acid.Compare, use the addition of transition metal complex catalytic amine and carbodiimide to synthesize the characteristics that guanidine compound has Atom economy, thereby develop very fast.Xie Zuowei etc. have reported the half sandwich complex-catalyzed amine of carborane metal titanium amido and the guanidine reaction of carbodiimide, and high productivity obtains polysubstituted guanidine compound.This catalyzer has broad applicability to substrate, and aromatic amine and aliphatic amide etc. is all had preferably catalytic activity (H.Shen, H.-S.Chan, Z.Xie, Organometallics 2006,25,5515).Complex structure is as follows:
People such as Hou Zhaomin have reported the half sandwich cyclopentadienyl rare earth metal alkyl compound catalysis catalytic amine and the guanidine reaction of carbodiimide, to aromatic amine (containing assorted aromatic amine) and aliphatic amide (containing cycloaliphatic amine) etc. all with higher yields obtain polysubstituted guanidine (W.-X.Zhang, M.Ni shiura, Z.Hou, Chem.Eur.J.2007,13,4037).Complex structure is as follows:
People such as Wang Shaowu utilize rare earth metal amido title complex [(Me
3Si)
2N]
3Ln
III(the Li (THF) of μ-Cl)
3The guanidine reaction of (Ln=yttrium and lanthanide series metal) catalytic amine and carbodiimide has obtained reaction result (Q.H.Li, S.W.Wang, S.L. Zhou preferably to aromatic amine and aliphatic amide, G.S.Yang, X.C.Zhu, Y.Y.Liu, J.Org.Chem.2007,72,6763).
Subsequently, people such as Wang Shaowu utilize the guanidine reaction of ethidene bridged linkage indenyl rareearth metal amine basigamy compound catalytic amine and carbodiimide again, also obtain polysubstituted guanidine compound (S.L.Zhou with higher productive rate, S.W.Wang, G.S.Yang, Q.H Li, L.J.Zhang, Z.J.Yao, Z.K.Zhou, H.B.Song, Organometallics 2007,26,3755).Complex structure is as follows:
Summary of the invention
The object of the invention provides a kind of aromatic amino methylene pyrrole ligand rare earth metal aminate that contains.
Another object of the present invention is the preparation method of above-mentioned metal aminate.
Another object of the present invention is the application of above-mentioned metal aminate.
The structure that contains aromatic amino methylene pyrrole ligand rare earth metal aminate provided by the invention is as follows:
In the formula, Ln is yttrium and lanthanide series metal, R
1～R
3Be H, C
1～C
4The straight or branched alkyl; R
4, R
5Be H or C
1～C
4Straight or branched alkyl or aromatic base; R
6Be C
1～C
4The straight or branched alkyl is silica-based, aromatic base is silica-based or substituted aromatic base is silica-based or C
1～C
4Straight or branched alkyl or aromatic base or substituted aromatic base.
Described C
1～C
4Straight chain is methyl, ethyl, propyl group, and butyl, branched hydrocarbyl are sec.-propyl, isobutyl-.
R wherein
1, R
2And R
3Can be identical or different, preferred R
1, R
2, R
3Be methyl.
Preferred R
4Be H, R
6Be two (trimethyl silicane) amido [(Me
3Si)
2N-].
The above-mentioned preparation method who contains aromatic amino pyrrole ligand rare earth metal aminate is: with aromatic amino methylene pyrrole and trivalent rare earth metals amido title complex [(Me
3Si)
2N]
3Ln
III(the Li (THF) of μ-Cl)
3(Ln=yttrium and lanthanide series metal) obtains by replacement(metathesis)reaction in organic solvent.Specifically finish by following reaction method:
By structural formula be
Aromatic amino methylene pyrrole and [(Me
3Si)
2N]
3Ln
III(the Li (THF) of μ-Cl)
3(Ln=yttrium and lanthanide series metal) is by 1: the mol ratio of 1-1.2, in organic solvent, to react 12～24 hours, and temperature of reaction is 60～110 ℃, can obtain containing the rare earth metal complex of respective ligand.
Described organic solvent is toluene, normal hexane.
The above-mentioned catalyzer that aromatic amino methylene pyrrole ligand rare earth metal aminate can be used for synthesising macromolecule copolymer that contains of the present invention is especially for the polymerization of catalysis rac-Lactide, valerolactone, caprolactone.Has the catalytic activity height, the characteristics of gained narrow molecular weight distribution.Concrete using method is: in the organic solvent that is dissolved with the prepared catalyzer of the present invention, add polymerization single polymerization monomer,-30～60 ℃ the reaction 0.5 minute after, add the industrial methanol termination reaction, then polymkeric substance is drained, use a small amount of (Chinese) THF dissolving again, go out polymkeric substance with industrial methanol extraction, drying obtains polymkeric substance under vacuum.
Described organic solvent is tetrahydrofuran (THF) or toluene or glycol dimethyl ether.
The above-mentioned addition reaction that aromatic amino methylene pyrrole ligand rare earth metal aminate also can be used for catalysis aromatic amine and carbodiimide that contains of the present invention.Particularly but the addition reaction of different substituted aroma amine compound of Atom economy catalysis and carbodiimide has the reaction conditions gentleness, and is active high, the characteristics that by product is few.
Described organic solvent is tetrahydrofuran (THF) or toluene.
The present invention compared with prior art, it is simple to have technology, the characteristics that the catalytic activity of made catalyzer is high.
Embodiment
Non-limiting examples is described below:
Intermediate [(Me
3Si)
2N]
3Ln
III(the Li (THF) of μ-Cl)
3The literature method that the preparation of (Ln=yttrium and lanthanide series metal) is published with reference to people such as Wang Shaowu (E.H.Sheng, S.W.Wang, G.S.Yang, S.L.Zhou, L.Cheng, K.H.Zhang, Z.X.Huang.Organometallics 2003,22, and 684).
Embodiment 1
At room temperature, (5.74g slowly drips 2 in 60.36mmol) to the 2-pyrrole aldehyde, (7.5mL 60.36mol), dropwises the 6-xylidine, in mixture, add 2.0mL formic acid, stirring at room 24 hours has a large amount of white solids to separate out, and filters, with 10.0mL * 3 methanol wash solids, use the normal hexane recrystallization again, vacuum-drying get white crystal 2-(2,6-Me
2C
6H
3N=CH) C
4H
3NH (11.37g, 95%).Results of elemental analyses (%): calculated value (C
13H
14N
2): C, 78.75; H, 7.12; N, 14.13.Measured value: C, 78.51; H, 7.02; N, 14.09.
Embodiment 2
At room temperature, to contain 2-(2,6-Me
2C
6H
3N=CH) C
4H
3(6.0g 30.26mmol) in the methanol solution of (embodiment 1), slowly adds NaBH to NH
4(2.29g, 60.52mol), solution acutely seethes with excitement, and treats that solution is cooled to room temperature, continues to stir 12 hours.After reaction finishes, the NH of slow impouring 20.0mL in reaction solution
4Cl aqueous solution termination reaction, reaction mixture 30.0mL extracted with diethyl ether, water is used 20.0mL * 2 extracted with diethyl ether twice again, merges organic phase, and uses anhydrous MgSO
4Drying is filtered, and vacuum is taken out and desolvated, with an amount of normal hexane recrystallization obtain white crystal 2-(2,6-Me
2C
6H
3NHCH
2) C
4H
3NH (5.45g, 90%).
Embodiment 3
To containing [(Me
3Si)
2N]
3Y (the Li (THF) of μ-Cl)
3(1.85g, 2.23mmol) in the 40.0mL toluene solution of (intermediate), slowly add 2-(2,6-Me
2C
6H
3NHCH
2) C
4H
3(110 ℃ of heated and stirred reactions 24 hours, reaction mixture was gradually by the colourless pale yellow solution that becomes for 0.45g, 2.23mmol) the 10.0mL toluene solution of (embodiment 2) for NH.Take out toluene, obtain colorless solid.Extract with 20.0mL normal hexane and toluene mixed solvent, the filtrate of gained is concentrated into about 10.0mL.Leave standstill at 0 ℃, obtain clear crystal 0.83g, productive rate 80%.Results of elemental analyses (%): calculated value (C
38H
64N
6Si
4Y
2THF): C, 52.15; H, 7.50; N, 8.69.Measured value: C, 52.28; H, 7.36; N, 9.02.
Its structural formula is:
Embodiment 4
To containing [(Me
3Si)
2N]
3Nd
III(the Li (THF) of μ-Cl)
3(2.35g, in 40.0mL toluene solution 2.66mmol), slowly add 2-(2,6-Me
2C
6H
3NHCH
2) C
4H
3(110 ℃ of heated and stirred reactions 24 hours, reaction mixture was gradually by the colourless pale yellow solution that becomes for 0.53g, 10.0mL toluene solution 2.66mmol) for NH.Toluene is taken out in decompression, obtains colorless solid.Extract with 20.0mL normal hexane and toluene mixed solvent, the filtrate of gained is concentrated into about 10.0mL.Leave standstill at 0 ℃, obtain blue crystal 1.04g, productive rate 75%.Results of elemental analyses (%): calculated value (C
38H
64N
6Si
4Nd
2): C, 45.38; H, 6.41; N, 8.36.Measured value: C, 45.85; H, 6.31; N, 8.42.
Its structural formula is:
Embodiment 5
To containing [(Me
3Si)
2N]
3Sm
III(the Li (THF) of μ-Cl)
3(1.75g, in 40.0mL toluene solution 1.97mmol), slowly add contain compound 2-(2,6-Me
2C
6H
3NHCH
2) C
4H
3(110 ℃ of heated and stirred reactions 24 hours, reaction mixture was gradually by the light yellow red solution that becomes for 0.39g, 10.0mL toluene solution 1.97mmol) for NH.Take out toluene, obtain red solid.Extract with 15.0mL normal hexane and toluene mixed solvent, the filtrate of gained is concentrated into about 10mL.Leave standstill at 0 ℃, obtain xanchromatic crystal 0.85g, productive rate 82%.Results of elemental analyses (%), calculated value (C
38H
64N
6Si
4Sm
2): C, 44.83; H, 6.34; N, 8.26.Measured value: C, 44.86; H, 6.16; N, 8.12.
Its structural formula is:
Embodiment 6
To containing [(Me
3Si)
2N]
3Dy (the Li (THF) of μ-Cl)
3(1.87g, in 40.0mL toluene solution 2.07mmol), slowly add contain compound 2-(2,6-Me
2C
6H
3NHCH
2) C
4H
3(110 ℃ of heated and stirred reactions 24 hours, reaction mixture was gradually by the light yellow red solution that becomes for 0.41g, 10.0mL toluene solution 2.07mmol) for NH.Take out toluene, obtain red solid.Extract with 15.0mL normal hexane and toluene mixed solvent, the filtrate of gained is concentrated into about 10.0mL.Leave standstill at 0 ℃, obtain colourless crystalline solid 0.84g, productive rate 78%.Results of elemental analyses (%): calculated value (C
38H
64N
6Si
4Dy
2): C, 43.79; H, 6.19; N, 8.06.Measured value: C, 43.98; H, 6.04; N, 7.63.
Its structural formula is:
Embodiment 7
To containing [(Me
3Si)
2N]
3Yb (the Li (THF) of μ-Cl)
3(2.06g, in 40.0mL toluene solution 2.26mmol), slowly add contain compound 2-(2,6-Me
2C
6H
3NHCH
2) C
4H
3(110 ℃ of heated and stirred reactions 24 hours, reaction mixture was gradually by the light yellow red solution that becomes for 0.45g, 10.0mL toluene solution 2.26mmol) for NH.Take out toluene, obtain red solid.Extract with 15.0mL normal hexane and toluene mixed solvent, the filtrate of gained is concentrated into about 10.0mL.Leave standstill at 0 ℃, obtain a red crystals 1.02g, productive rate 85%.Results of elemental analyses (%): calculated value (C
38H
64N
6Si
4Yb
2): C, 42.92; H, 6.07; N, 7.90.Measured value: C, 43.38; H, 5.83; N, 7.88.
Its structural formula is:
Embodiment 8
At room temperature, to be dissolved with the 2-pyrrole aldehyde (5.00g, in methanol solution 52.58mmol), disposable adding is new steam 2,4,6-Me
3PhNH
2(7.38ml 52.58mmol), adds 2.0mL formic acid in mixture, stirring reaction is 6 hours under the room temperature, has a large amount of white powder solids to generate, the elimination mother liquor, with the adequate amount of ethanol recrystallization obtain the white plates crystal 2-(2,4,6-Me
3C
6H
2N=CH) C
4H
3NH (10.35g, 91%).Results of elemental analyses (%): calculated value (C
14H
16N
2): C, 79.21; H, 7.60; N, 13.20.Measured value: C, 79.33; H, 7.32; N, 13.27.
Embodiment 9
At room temperature, to be dissolved with 2-(2,4,6-Me
3C
6H
2N=CH) C
4H
3(5.00g 23.55mmol) in the methanol solution of (embodiment 8), slowly adds NaBH to NH
4(1.78g 47.10mol) reduces, and makes solution remain slight boiling condition, at room temperature reacts 12 hours again.After reaction finishes, add excessive saturated ammonium chloride solution neutralization in reaction solution, use the 40.0mL extracted with diethyl ether again, water is used 2 * 20.0mL Et again
2The O extracting twice merges organic phase, adds anhydrous Na
2SO
4Drying is filtered, take out and desolvate, with an amount of normal hexane recrystallization obtain white crystalline solid 2-(2,4,6-Me
3C
6H
2NHCH
2) C
4H
3NH (4.49g, 89%).Results of elemental analyses (%): calculated value (C
14H
18N
2): C, 78.46; H, 8.47; N, 13.07.Measured value: C, 78.58; H, 8.62; N, 13.07.
Embodiment 10
To be dissolved with compound 2-(2,4,6-Me
3C
6H
2NHCH
2) C
4H
3(0.44g 2.05mmol) adds [(Me to NH in the 40.0mL toluene solution of (embodiment 9)
3Si)
2N]
3Y
III(the Li (THF) of μ-Cl)
3(1.70g, 2.05mmol), 110 ℃ of heated and stirred reaction 24 hours, the reaction mixture color gradually by colourless become light yellow.Vacuum is taken out toluene, obtains the colorless solid material, uses the 15.0mL normal hexane extraction, obtains light yellow settled solution, leaves standstill under the room temperature, obtains clear crystal 1.50g, productive rate 79%.Results of elemental analyses (%): calculated value (C
40H
68N
6Si
4Y
2): C, 52.04; H, 7.42; N, 9.10.Measured value: C, 52.11; H, 7.34; N, 8.96.
Its structural formula is:
Embodiment 11
To be dissolved with compound 2-(2,4,6-Me
3C
6H
2NHCH
2) C
4H
3(0.39g adds [(Me to NH in 40mL toluene solution 1.83mmol)
3Si)
2N]
3Nd
III(the Li (THF) of μ-Cl)
3(1.62g, 1.83mmol), 110 ℃ of heated and stirred reactions 24 hours, the reaction mixture color was gradually by the light blue grass green that becomes.Vacuum is taken out toluene, obtains the green solid material, uses the 15.0mL normal hexane extraction, obtains green settled solution, leaves standstill under the room temperature, obtains a green flour powder solid matter 1.34g, productive rate 71%.Results of elemental analyses (%): calculated value (C
40H
68N
6Si
4Nd
2): C, 46.47; H, 6.63; N, 8.13.Measured value: C, 46.05; H, 6.70; N, 8.13.
Its structural formula is:
Embodiment 12
To be dissolved with compound 2-(2,4,6-Me
3C
6H
2NHCH
2) C
4H
3(0.35g adds [(Me to NH in 40mL toluene solution 1.65mmol)
3Si)
2N]
3Sm
III(the Li (THF) of μ-Cl)
3(1.47g, 1.65mmol), 110 ℃ of heated and stirred reactions 24 hours, the reaction mixture color was gradually by the faint yellow redness that becomes.Vacuum is taken out toluene, obtains yellow solid matter, uses the 15.0mL normal hexane extraction, obtains red settled solution, leaves standstill under the room temperature, obtains yellow crystals 1.43g, productive rate 83%.Results of elemental analyses (%): calculated value (C
40H
68N
6Si
4Sm
2): C, 45.93; H, 6.55; N, 8.03.Measured value: C, 45.91; H, 6.66; N, 8.16.
Its structural formula is:
Embodiment 13
To be dissolved with compound 2-(2,4,6-Me
3C
6H
2NHCH
2) C
4H
3(0.43g adds [(Me to NH in 40mL toluene solution 2.01mmol)
3Si)
2N]
3Dy
III(the Li (THF) of μ-Cl)
3(1.81g, 2.00mmol), 110 ℃ of heated and stirred reaction 24 hours, the reaction mixture color gradually by colourless become light yellow.Take out toluene, obtain the colorless solid material, use the 15.0mL normal hexane extraction, obtain light yellow settled solution, leave standstill under the room temperature, obtain colourless powder shape solid matter 1.74g, productive rate 81%.Results of elemental analyses (%): calculated value (C
40H
68N
6Si
4Dy
2): C, 44.89; H, 6.40; N, 7.85.Measured value: C, 45.34; H, 6.07; N, 7.47.
Its structural formula is:
Embodiment 14
To be dissolved with compound 2-(2,4,6-Me
3C
6H
2NHCH
2) C
4H
3(0.38g adds [(Me to NH in 40mL toluene solution 1.76mmol)
3Si)
2N]
3Er
III(the Li (THF) of μ-Cl)
3(1.60g, 1.76mmol), 110 ℃ of heated and stirred reactions 24 hours, the reaction mixture color was gradually by the light yellow pink that becomes.Take out toluene, obtain the pink solid material, use the 15.0mL normal hexane extraction, obtain the light red settled solution, leave standstill under the room temperature, obtain pink crystal 1.43g, productive rate 75%.Results of elemental analyses (%): calculated value (C
40H
68N
6Si
4Er
2): C, 44.49; H, 6.35; N, 7.78.Measured value: C, 45.00; H, 5.96; N, 7.70.
Its structural formula is:
Embodiment 15
Title complex (20-40mg) is dissolved in toluene or the tetrahydrofuran (THF), make it temperature maintenance to reaction temperature required (seeing Table middle temperature), disposable then adding monomer is after reaction finishes, stop polyreaction with acidic methanol, obtain polymkeric substance through carrying out recrystallization with methyl alcohol or normal hexane solvent.
M in the table
nBe number-average molecular weight, M
wBe weight-average molecular weight, M
w/ M
NyBe molecular weight distribution.
Table 1{[(η
5: η
1-2-(2,6-Me
3PhNCH
2) (C
4H
3N)] YN (SiMe
3)
2}
2(embodiment 3) catalysis L-rac-Lactide polymerization activity
| L-rac-Lactide/catalyzer (mol/mol) | Temperature (℃) | Time (min) | ??Mn??×10 -4 | ??Mw??×10 -4 | ??Mw/Mn | Transformation efficiency (%) | Active (* 10 6) |
| ??500∶1 | ??60 | ??1 | ??3.28 | ??6.13 | ??1.87 | ??87 | ??3.76 |
| ??500∶1 | ??40 | ??1 | ??3.47 | ??6.28 | ??1.81 | ??73 | ??3.15 |
| ??500∶1 | ??20 | ??1 | ??4.46 | ??7.02 | ??1.57 | ??36 | ??1.55 |
| ??300∶1 | ??60 | ??1 | ??2.65 | ??4.95 | ??1.87 | ??95 | ??2.47 |
| ??300∶1 | ??40 | ??1 | ??2.88 | ??5.35 | ??1.85 | ??90 | ??2.34 |
| ??300∶1 | ??20 | ??1 | ??3.39 | ??6.16 | ??1.82 | ??65 | ??1.68 |
| ??200∶1 | ??60 | ??1 | ??2.18 | ??5.07 | ??1.76 | ??98 | ??1.69 |
| ??200∶1 | ??40 | ??1 | ??3.02 | ??5.49 | ??1.82 | ??97 | ??1.67 |
| ??200∶1 | ??20 | ??1 | ??3.40 | ??6.20 | ??1.82 | ??75 | ??1.30 |
Solvent for use: toluene; [L-rac-Lactide]=1mol/L; Reaction times: 1min; Active: g polymkeric substance/mol catalyzer hour.
Table 2{[(η
5: η
1-2-(2,6-Me
3PhNCH
2) (C
4H
3N)] SmN (SiMe
3)
2}
2(embodiment 5) catalysis L-rac-Lactide polymerization activity
| L-rac-Lactide/catalyzer (mol/mol) | Temperature (℃) | ??M n×10 -4 | ??M w×10 -4 | ??M w/M n | Transformation efficiency (%) | Active (* 10 6) |
| ??500∶1 | ??60 | ??3.07 | ??5.56 | ??1.81 | ??97 | ??4.18 |
| ??500∶1 | ??40 | ??3.12 | ??5.67 | ??1.82 | ??84 | ??3.62 |
| ??500∶1 | ??20 | ??3.84 | ??6.63 | ??1.73 | ??36 | ??1.55 |
| ??300∶1 | ??60 | ??2.79 | ??5.01 | ??1.80 | ??85 | ??2.21 |
| ??300∶1 | ??40 | ??2.83 | ??5.11 | ??1.80 | ??67 | ??1.74 |
| ??300∶1 | ??20 | ??3.16 | ??5.81 | ??1.84 | ??26 | ??0.67 |
| L-rac-Lactide/catalyzer (mol/mol) | Temperature (℃) | ??M n×10 -4 | ??M w×10 -4 | ??M w/M n | Transformation efficiency (%) | Active (* 10 6) |
| ??200∶1 | ??60 | ??2.77 | ??4.95 | ??1.78 | ??91 | ??1.57 |
| ??200∶1 | ??40 | ??2.82 | ??5.04 | ??1.79 | ??87 | ??1.50 |
| ??200∶1 | ??20 | ??3.39 | ??6.05 | ??1.79 | ??33 | ??0.57 |
Solvent for use: toluene; [L-rac-Lactide]=1mol/L; Reaction times: 1min; Active: g polymkeric substance/mol catalyzer hour.
Table 3{[(η
5: η
1-2-(2,6-Me
3PhNCH
2) (C
4H
3N)] DyN (SiMe
3)
2}
2(embodiment 6) catalysis L-rac-Lactide polymerization activity
| L-rac-Lactide/catalyzer (mol/mol) | Temperature (℃) | ??M n×10 -4 | ??M w×10 -4 | ??M w/M n | Transformation efficiency (%) | Active (* 10 6) |
| ??500∶1 | ??60 | ??2.20 | ??5.37 | ??1.79 | ??93 | ??4.01 |
| ??500∶1 | ??40 | ??3.10 | ??5.61 | ??1.81 | ??85 | ??3.67 |
| ??500∶1 | ??20 | ??3.08 | ??5.68 | ??1.84 | ??41 | ??1.77 |
| ??300∶1 | ??60 | ??2.95 | ??5.29 | ??1.79 | ??96 | ??2.47 |
| ??300∶1 | ??40 | ??2.97 | ??5.31 | ??1.79 | ??86 | ??2.21 |
| ??300∶1 | ??20 | ??3.23 | ??5.96 | ??1.84 | ??45 | ??1.15 |
| ??200∶1 | ??60 | ??2.84 | ??5.09 | ??1.79 | ??99 | ??1.71 |
| ??200∶1 | ??40 | ??2.85 | ??5.17 | ??1.82 | ??80 | ??1.38 |
| ??200∶1 | ??20 | ??2.89 | ??5.24 | ??1.81 | ??53 | ??0.92 |
Solvent for use: toluene; [L-rac-Lactide]=1mol/L; Reaction times: 1min; Active: g polymkeric substance/mol catalyzer hour.
Table 4{[(η
5: η
1-2-(2,6-Me
3PhNCH
2) (C
4H
3N)] YbN (SiMe
3)
2}
2(embodiment 7) catalysis L-LA polymerization activity
| L-rac-Lactide/catalyzer (mol/mol) | Temperature (℃) | ??M n×10 -4 | ??M w×10 -4 | ??M w/M n | Transformation efficiency (%) | Active (* 10 6) |
| ??500∶1 | ??60 | ??3.22 | ??5.67 | ??1.76 | ??94 | ??4.06 |
| ??500∶1 | ??40 | ??3.72 | ??6.57 | ??1.76 | ??84 | ??3.62 |
| ??500∶1 | ??20 | ??4.18 | ??7.26 | ??1.81 | ??56 | ??2.41 |
| ??300∶1 | ??60 | ??3.17 | ??5.76 | ??1.82 | ??94 | ??2.44 |
| ??300∶1 | ??40 | ??3.20 | ??5.76 | ??1.80 | ??86 | ??2.23 |
| ??300∶1 | ??20 | ??3.45 | ??6.20 | ??1.79 | ??43 | ??1.12 |
| ??200∶1 | ??60 | ??2.46 | ??4.18 | ??1.70 | ??92 | ??1.59 |
| ??200∶1 | ??40 | ??2.78 | ??4.91 | ??1.77 | ??85 | ??1.47 |
| ??200∶1 | ??20 | ??2.82 | ??5.04 | ??1.78 | ??45 | ??0.78 |
Solvent for use: toluene; [L-rac-Lactide]=1mol/L; Reaction times: 1min; Active: g polymkeric substance/mol catalyzer hour
Embodiment 15
Table 5{[(η
5: η
1-(2,6-Me
3PhNCH
2) (C
4H
3N)] YN (SiMe
3)
2}
2(embodiment 3) catalysis 6-caprolactone polymerization activity
| Catalyzer/monomer (mol/mol) | Solvent | Temperature (℃) | ??M n×10 -4 | ??M w×10 -4 | ??M w/M n | Transformation efficiency (%) | Active (* 10 6) |
| ??1∶500 | Toluene | ??30 | ??2.87 | ??5.20 | ??1.81 | ??98 | ??6.85 |
| ??1∶500 | Toluene | ??0 | ??2.90 | ??5.34 | ??1.79 | ??92 | ??6.43 |
| ??1∶500 | Toluene | ??-30 | ??2.99 | ??5.34 | ??1.84 | ??70 | ??4.89 |
| ??1∶500 | Toluene | ??-60 | ??5.90 | ??7.40 | ??1.26 | ??34 | ??2.38 |
| ??1∶500 | Tetrahydrofuran (THF) | ??30 | ??2.06 | ??3.45 | ??1.67 | ??86 | ??6.02 |
| ??1∶500 | Tetrahydrofuran (THF) | ??0 | ??2.37 | ??4.22 | ??1.78 | ??76 | ??5.32 |
| ??1∶500 | Tetrahydrofuran (THF) | ??-30 | ??2.73 | ??5.06 | ??1.86 | ??65 | ??4.55 |
| Catalyzer/monomer (mol/mol) | Solvent | Temperature (℃) | ??M n×10 -4 | ??M w×10 -4 | ??M w/M n | Transformation efficiency (%) | Active (* 10 6) |
| ??1∶500 | Tetrahydrofuran (THF) | ??-60 | ??2.81 | ??5.15 | ??1.83 | ??26 | ??1.82 |
| ??1∶300 | Toluene | ??30 | ??2.52 | ??4.43 | ??1.76 | ??93 | ??3.84 |
| ??1∶300 | Toluene | ??0 | ??2.66 | ??4.77 | ??1.80 | ??88 | ??3.63 |
| ??1∶300 | Toluene | ??-30 | ??2.80 | ??5.16 | ??1.85 | ??74 | ??3.06 |
| ??1∶300 | Toluene | ??-60 | ??2.87 | ??5.19 | ??1.81 | ??46 | ??1.90 |
| ??1∶300 | Tetrahydrofuran (THF) | ??30 | ??2.00 | ??3.10 | ??1.55 | ??91 | ??3.76 |
| ??1∶300 | Tetrahydrofuran (THF) | ??0 | ??2.08 | ??3.49 | ??1.68 | ??89 | ??3.67 |
| ??1∶300 | Tetrahydrofuran (THF) | ??-30 | ??2.53 | ??4.44 | ??1.76 | ??65 | ??2.68 |
| ??1∶300 | Tetrahydrofuran (THF) | ??-60 | ??2.53 | ??4.66 | ??1.84 | ??32 | ??1.32 |
Solvent/monomer (mol/mol)=5: 1; Active: g polymkeric substance/mol catalyzer hour.
Table 6[[(η
5: η
1-2-(2,6-Me
3PhNCH
2) (C
4H
3N)] NdN (SiMe
3)
2}
2(embodiment 4) catalysis 6-caprolactone polymerization activity
| Catalyzer/monomer (mol/mol) | Solvent | Temperature (℃) | ??M n×10 -4 | ??M w×10 -4 | ??M w/M n | Transformation efficiency (%) | Active (* 10 6) |
| ??1∶500 | Toluene | ??30 | ??2.81 | ??5.20 | ??1.85 | ??99 | ??6.93 |
| ??1∶500 | Toluene | ??0 | ??2.91 | ??5.29 | ??1.82 | ??98 | ??6.86 |
| ??1∶500 | Toluene | ??-30 | ??2.92 | ??5.31 | ??1.81 | ??62 | ??4.34 |
| ??1∶500 | Toluene | ??-60 | ??2.95 | ??5.51 | ??1.86 | ??33 | ??2.31 |
| ??1∶500 | Tetrahydrofuran (THF) | ??30 | ??2.92 | ??5.27 | ??1.81 | ??80 | ??5.60 |
| ??1∶500 | Tetrahydrofuran (THF) | ??0 | ??2.95 | ??5.43 | ??1.84 | ??64 | ??4.48 |
| ??1∶500 | Tetrahydrofuran (THF) | ??-30 | ??3.12 | ??5.61 | ??1.80 | ??57 | ??3.99 |
| ??1∶500 | Tetrahydrofuran (THF) | ??-60 | ??3.25 | ??5.79 | ??1.78 | ??26 | ??1.82 |
| Catalyzer/monomer (mol/mol) | Solvent | Temperature (℃) | ??M n×10 -4 | ??M w×10 -4 | ??M w/M n | Transformation efficiency (%) | Active (* 10 6) |
| ??1∶300 | Toluene | ??30 | ??2.64 | ??4.83 | ??1.83 | ??98 | ??4.06 |
| ??1∶300 | Toluene | ??0 | ??2.67 | ??4.78 | ??1.79 | ??92 | ??3.79 |
| ??1∶300 | Toluene | ??-30 | ??2.76 | ??5.01 | ??1.82 | ??78 | ??3.21 |
| ??1∶300 | Toluene | ??-60 | ??2.96 | ??5.39 | ??1.82 | ??31 | ??1.28 |
| ??1∶300 | Tetrahydrofuran (THF) | ??30 | ??2.30 | ??4.00 | ??1.73 | ??86 | ??3.54 |
| ??1∶300 | Tetrahydrofuran (THF) | ??0 | ??2.55 | ??4.65 | ??1.82 | ??80 | ??3.30 |
| ??1∶300 | Tetrahydrofuran (THF) | ??-30 | ??2.72 | ??4.72 | ??1.74 | ??56 | ??2.31 |
| ??1∶300 | Tetrahydrofuran (THF) | ??-60 | ??2.78 | ??4.84 | ??1.74 | ??26 | ??1.07 |
Solvent/monomer (mol/mol)=5: 1; Active: g polymkeric substance/mol catalyzer hour.
Table 7{[(η
5: η
1-2-(2,6-Me
3PhNCH
2) (C
4H
3N)] SmN (SiMe
3)
2}
2(embodiment 5) catalysis 6-caprolactone polymerization activity
| Catalyzer/monomer (mol/mol) | Solvent | Temperature (℃) | ??M n×10 -4 | ??M w×10 -4 | ??M w/M n | Transformation efficiency (%) | Active (* 10 6) |
| ??1∶500 | Toluene | ??30 | ??2.17 | ??3.28 | ??1.51 | ??97 | ??6.79 |
| ??1∶500 | Toluene | ??0 | ??2.31 | ??4.30 | ??1.86 | ??88 | ??6.16 |
| ??1∶500 | Toluene | ??-30 | ??4.70 | ??7.03 | ??1.50 | ??71 | ??4.97 |
| ??1∶500 | Toluene | ??-60 | ??5.50 | ??7.09 | ??1.29 | ??46 | ??3.22 |
| ??1∶500 | ??THF | ??30 | ??2.06 | ??3.53 | ??1.72 | ??91 | ??6.37 |
| ??1∶500 | ??THF | ??0 | ??2.20 | ??3.60 | ??1.64 | ??84 | ??5.88 |
| ??1∶500 | ??THF | ??-30 | ??2.59 | ??4.52 | ??1.74 | ??63 | ??4.41 |
| ??1∶500 | ??THF | ??-60 | ??2.73 | ??4.98 | ??1.82 | ??38 | ??2.66 |
| ??1∶300 | Toluene | ??30 | ??2.64 | ??4.83 | ??1.83 | ??98 | ??4.06 |
| Catalyzer/monomer (mol/mol) | Solvent | Temperature (℃) | ??M n×10 -4 | ??M w×10 -4 | ??M w/M n | Transformation efficiency (%) | Active (* 10 6) |
| ??1∶300 | Toluene | ??0 | ??2.67 | ??4.78 | ??1.79 | ??92 | ??3.79 |
| ??1∶300 | Toluene | ??-30 | ??2.76 | ??5.01 | ??1.82 | ??78 | ??3.21 |
| ??1∶300 | Toluene | ??-60 | ??2.96 | ??5.39 | ??1.82 | ??31 | ??1.28 |
| ??1∶300 | ??THF | ??30 | ??2.30 | ??4.00 | ??1.73 | ??86 | ??3.54 |
| ??1∶300 | ??THF | ??0 | ??2.55 | ??4.65 | ??1.82 | ??80 | ??3.30 |
| ??1∶300 | ??THF | ??-30 | ??2.72 | ??4.72 | ??1.74 | ??56 | ??2.31 |
| ??1∶300 | ??THF | ??-60 | ??2.78 | ??4.84 | ??1.74 | ??26 | ??1.07 |
Solvent/monomer (mol/mol)=5: 1; Active: g polymkeric substance/mol catalyzer hour.
Embodiment 16
In the tetrahydrofuran solvent of title complex and aromatic amine, the mol ratio of title complex and aromatic amine is 2%, adds RN=C=NR (R=cyclohexyl or sec.-propyl), reacts 12 hours down at 60 ℃.Adding 3mL water termination reaction, reaction solution 30.0mL dichloromethane extraction, water are used methylene dichloride again, and (2 * 10mL) extracting twice merge organic phase, and use anhydrous sodium sulfate drying, filter.The decompressing and extracting solvent gets corresponding polysubstituted guanidine compound with ether or normal hexane recrystallization.
Table 8{[(η
5: η
1-2-(2,4,6-Me
3PhNCH
2) (C
4H
3N)] SmN (SiMe
3)
2}
2The addition reaction of (embodiment 12) catalysis aromatic amine and carbodiimide
Title complex: 0.02mol; Aromatic amine: 1mol; Cy is a cyclohexyl,
iPr is a sec.-propyl; Solvent for use: tetrahydrofuran (THF) (5mL).
Claims (8)
1. contain aromatic amino methylene pyrrole ligand rare earth metal aminate, its structure is as follows:
In the formula, Ln is yttrium and lanthanide series metal, R
1, R
2, R
3Be H, C
1～C
4The straight or branched alkyl; R
4, R
5Be H or C
1～C
4Straight or branched alkyl or aromatic base; R
6Be C
1～C
4The straight or branched alkyl is silica-based, aromatic base is silica-based or substituted aromatic base is silica-based or C
1～C
4Straight or branched alkyl or aromatic base or substituted aromatic base.
2. the aromatic amino methylene pyrrole ligand rare earth metal aminate that contains according to claim 1 is characterized in that: described C
1～C
4Straight chain is methyl, ethyl, propyl group, butyl; Branched hydrocarbyl is sec.-propyl, isobutyl-.
3. the aromatic amino methylene pyrrole ligand rare earth metal aminate that contains according to claim 1 is characterized in that: described R
1, R
2, R
3Be methyl.
4. the aromatic amino methylene pyrrole ligand rare earth metal aminate that contains according to claim 1 is characterized in that: described R
4Be H, R
6It is two (trimethyl silicane) amido.
5. the described preparation method who contains aromatic amino pyrrole ligand rare earth metal aminate of claim 1 is:
By structural formula be
The aromatic amino methylene pyrrole with
[(Me
3Si)
2N]
3Ln
III(the Li (THF) of μ-Cl)
3(Ln=yttrium and lanthanide series metal) is by 1: the mol ratio of 1-1.2, in organic solvent, to react 12～24 hours, and temperature of reaction is 60～110 ℃, can obtain containing the rare earth metal complex of respective ligand.
6. the described preparation method of claim 5, it is characterized in that: described organic solvent is normal hexane, toluene.
7. the described application that contains aromatic amino pyrrole ligand rare earth metal aminate at synthesising macromolecule copolymer of claim 1.
8. the described application that contains aromatic amino pyrrole ligand rare earth metal aminate in the addition reaction of catalysis aromatic amine and carbodiimide of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101402668A CN101812084B (en) | 2010-03-31 | 2010-03-31 | Rare earth metal amine compound containing aromatic amine methylene pyrrole ligand, preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102002070A (en) * | 2010-10-15 | 2011-04-06 | 安徽师范大学 | Calix [4] pyrrole ligand rare-earth metal complex, preparation method and application thereof |
| CN102380419A (en) * | 2011-09-15 | 2012-03-21 | 安徽师范大学 | Catalyst for synthesizing hydroxyl phosphate, preparation and use method thereof |
| CN109012748A (en) * | 2018-07-27 | 2018-12-18 | 安徽师范大学 | Pyridine substituted azole base rare-earth metal catalyst and its preparation method and application |
| CN109225335A (en) * | 2018-07-27 | 2019-01-18 | 安徽师范大学 | rare earth metal catalyst containing non-classical α -diimine dicarbanion ligand and preparation method and application thereof |
| CN113061290A (en) * | 2021-04-09 | 2021-07-02 | 常州佑佳新材料科技有限公司 | Nitrogen heterocyclic ring rare earth stabilizer |
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| CN1583733A (en) * | 2004-05-31 | 2005-02-23 | 安徽师范大学 | Bivalent rare earth complex containing oxacyclo substituted indene ligand and its use |
| CN1583761A (en) * | 2004-05-31 | 2005-02-23 | 安徽师范大学 | Bivalent rare earth complex containing pyridine substituted indene ligand and its use |
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| CN1583733A (en) * | 2004-05-31 | 2005-02-23 | 安徽师范大学 | Bivalent rare earth complex containing oxacyclo substituted indene ligand and its use |
| CN1583761A (en) * | 2004-05-31 | 2005-02-23 | 安徽师范大学 | Bivalent rare earth complex containing pyridine substituted indene ligand and its use |
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| 《安徽师范大学学报》 20070531 宋忠诚 等 含N-吗啉乙基茚基配体镱金属配合物的合成、表征及催化性能的研究 第266-269页 1-8 第30卷, 第3期 2 * |
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| CN102002070A (en) * | 2010-10-15 | 2011-04-06 | 安徽师范大学 | Calix [4] pyrrole ligand rare-earth metal complex, preparation method and application thereof |
| CN102002070B (en) * | 2010-10-15 | 2013-06-12 | 安徽师范大学 | Calix [4] pyrrole ligand rare-earth metal complex, preparation method and application thereof |
| CN102380419A (en) * | 2011-09-15 | 2012-03-21 | 安徽师范大学 | Catalyst for synthesizing hydroxyl phosphate, preparation and use method thereof |
| CN102380419B (en) * | 2011-09-15 | 2013-06-12 | 安徽师范大学 | Catalyst for synthesizing hydroxyl phosphate, preparation and use method thereof |
| CN109012748A (en) * | 2018-07-27 | 2018-12-18 | 安徽师范大学 | Pyridine substituted azole base rare-earth metal catalyst and its preparation method and application |
| CN109225335A (en) * | 2018-07-27 | 2019-01-18 | 安徽师范大学 | rare earth metal catalyst containing non-classical α -diimine dicarbanion ligand and preparation method and application thereof |
| CN109225335B (en) * | 2018-07-27 | 2021-03-12 | 安徽师范大学 | Rare earth metal catalyst containing non-classical alpha-diimine dicarbanion ligand and preparation method and application thereof |
| CN109012748B (en) * | 2018-07-27 | 2021-03-16 | 安徽师范大学 | Pyridine substituted pyrrole based rare earth metal catalyst and preparation method and application thereof |
| CN113061290A (en) * | 2021-04-09 | 2021-07-02 | 常州佑佳新材料科技有限公司 | Nitrogen heterocyclic ring rare earth stabilizer |
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