CN102702241A - Amino-bridged bis(aryloxide) rare earth metal alkoxy complexes as well as preparation and application thereof - Google Patents
Amino-bridged bis(aryloxide) rare earth metal alkoxy complexes as well as preparation and application thereof Download PDFInfo
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Abstract
The invention provides complexes shown in formula I, wherein Ln is rare earth metal; and R1 and R2 are hydrogen and methyl or tertiary butyl respectively. The complexes comprise rare earth elements and amino-bridged ligands, also comprise trifluoroethoxy, can effectively catalyze the ring-opening reaction, can increase reaction velocity, and can enable the reaction conditions to be milder. The invention also provides a preparation method of compounds and an application for preparing poly rac-Beta-butyrolactone and poly rac-lactide shown in formula I .
Description
Technical field
The present invention relates to the organometallics preparation field, be specifically related to a kind of amido bridged linkage bis aryloxy rare earth metal trifluoro ethoxy title complex and preparation and application.
Background technology
Since the catalysis cyclic ester class monomer ring-opening polymerization effectively of rare earth metal alkoxide complexes, and have excellent controllability, so the synthetic and catalytic performance research of rare earth metal alkoxide complexes has caused people's extensive interest.
2003, Carpentier seminar investigated the catalytic performance of side arm band methoxyl group amido bridged linkage bis aryloxy rare earth compound with regard to beginning.They find that corresponding aminate can cause the ring-opening polymerization of racemization rac-Lactide, exist under the condition of Virahol, and they can high reactivity ground catalysis rac-rac-Lactide and the controlled stereoselectivity polymerization of beta-butyrolactone, and the gained polylactide is high heterotactic polymer; Gather GBL and be main (referring to (a) A.Amgoune, C.M.Thomas, S.Ilinca with the syndiotactic; T.Roisnel and J.F.Carpentier, Angew.Chem., Int.Ed.; 2006,45,2782; (b) A.Amgoune, C.M.Thomas, T.Roisnel and J.F.Carpentier, Chem.Eur.J., 2006,12,169; (c) A.Amgoune, C.M.Thomas and J.F.Carpentier, Macromol.Rapid Commun., 2007,28,693.).
2007, Cui Dong Mei seminar utilized trialkyl rare earth compound and amido bridging bis-phenol generation alkyl to eliminate reaction, has synthesized corresponding rare earth metal trimethyl silicane methyl compound.These rare earth trimethyl silicane methyl compounds have shown catalytic activity preferably to the polymerization of rac-lactide, obtain high assorted with polymkeric substance, but in catalystsystem, add alcohol catalyzer is lost activity (referring to X.L.Liu, X.M.Shang; T.Tang, N.H.Hu, F.K.Pei; D.M.Cui, X.S.Chen and X.B.Jing, Organometallics; 2007,26,2747.).
2010; Cui Dong Mei group has reported that bridged linkage bis aryloxy rare earth trimethyl silicane methyl compound can cause the rac-Lactide polymerization under the condition that trolamine exists; The star polylactide that obtains having three arm configurations is (referring to W.Zhao; D.M.Cui and X.S.Chen.Macromolecules 2010,43,6678).
2009, Coates seminar has obtained first amido bridged linkage bis aryloxy yttrium isopropoxy compound through structural characterization through amido bridged linkage bis aryloxy yttrium aminate and isopropanol reaction, find its effectively the syndiotactic polymerization of catalysis beta-butyrolactone (referring to J.W.Kramer; D.S.Treitler, E.W.Dunn, P.M.Castro; T.Roisnel, C.M.Thomas and G.W.Coates, J.Am.Chem.Soc.; 2009,131,16042.).
Carbon bridged linkage bis aryloxy rare earth metal alkoxide complexes comprises benzyloxy compound, isopropoxy compound and methoxylation compound etc., can be through the exchange preparation of carbon bridged linkage bis aryloxy rare earth metal cyclopentadienyl compound with alcohol; This method raw material cheaply is easy to get, that product separation is purified is simple and convenient (referring to: (a) X.P.Xu, Y.M.Yao; Y.Zhang and Q.Shen, Inorg.Chem., 2007; 46,3743; (b) X.P.Xu, Y.M.Yao, Y.Zhang and Q.Shen, Chinese Sci.Bull., 2007,52,1623.).But amido bridged linkage bis aryloxy rare earth metal cyclopentadienyl compound and methyl alcohol, ethanol, Virahol and benzylalcohol but do not react, and can not prepare corresponding amido bridged linkage bis aryloxy rare earth metal alkoxide complexes (referring to L.Z.Zhou through this kind method; Y.M.Wang, Y.M.Yao, Y.Zhang; Q.Shen, J.Rare Earths, 2007; 25,544.).
Summary of the invention
The technical problem that the present invention will solve is to provide amido bridged linkage bis aryloxy rare earth metal trifluoro ethoxy title complex of the higher and easy preparation of a kind of catalytic activity and preparation method thereof, with and at catalyzed prepn of poly rac-beta-butyrolactone and gather the application in the rac-rac-Lactide.
In order to solve above technical problem, the invention provides the compound shown in a kind of formula I,
Formula I
Wherein, Ln is a rare earth metal; R
1And R
2Be respectively hydrogen, methyl or the tertiary butyl.
Preferably, said Ln is lanthanum, samarium, erbium, ytterbium or yttrium.
The present invention also provides a kind of formula I the preparation method of described title complex, comprising:
A) title complex shown in the formula II is provided;
B) substitution reaction is taken place in title complex shown in the formula II and trifluoroethanol in solvent, obtain the compound shown in the formula I;
Formula II
Wherein, Ln is a rare earth metal; R
1And R
2Be respectively hydrogen, methyl or the tertiary butyl.
Preferably, step a) is specially:
A1) with amido bridging bis-phenol shown in the formula III and tricyclopentadienyl rare earth compounding (C
5H
5)
3Ln (THF) is mixed with the title complex shown in the formula II;
Formula III
Wherein, R
1And R
2Be respectively hydrogen, methyl or the tertiary butyl.
Preferably, said Ln is lanthanum, samarium, erbium, ytterbium or yttrium.
Preferably, step b) is specially:
B1) under the anhydrous and oxygen-free condition, title complex and the trifluoroethanol shown in the formula II is blended in the solvent for 1:1 ~ 1.05 in molar ratio, substitution reaction 10 ~ 20h takes place, remove said solvent, obtain crude product;
B2) with the said crude product of extracted in toluene, remove deposition, concentrated extract obtains crystal under 0 ~ 5 ℃, i.e. compound shown in the formula I.
Preferably, said solvent is aromatic solvents or ether solvent.
Preferably, the temperature of substitution reaction described in the step b) is 40 ~ 60 ℃.
The present invention also provides a kind of preparation method of the rac-of gathering beta-butyrolactone, comprising:
With the title complex shown in the formula I and rac-beta-butyrolactone monomer is 1: 200～3000 to be blended in the solvent in molar ratio, obtains mixing solutions;
Ring-opening polymerization is taken place down at 10 ~ 70 ℃ in said mixing solutions, obtain gathering the rac-beta-butyrolactone.
The present invention also provides a kind of preparation method of the rac-of gathering rac-Lactide, comprising:
With the said title complex of formula I and rac-lactide monomer is 1: 200～3000 to be blended in the solvent in molar ratio, obtains mixing solutions;
Ring-opening polymerization is taken place down at 10 ~ 40 ℃ in said mixing solutions, obtain gathering the rac-rac-Lactide.
Compound provided by the invention, shown in I, owing to be amido bridged linkage bis aryloxy rare earth metal trifluoro ethoxy title complex, because the existence of amido bridge ligand, rare earth metal and alkoxyl group makes that its catalytic activity at the catalysis ring-opening polymerization is higher.
The present invention also provides the preparation method of the compound shown in a kind of formula I, through the title complex shown in the formula II a) is provided; B) substitution reaction is taken place in title complex shown in the formula II and trifluoroethanol in solvent, obtain the compound shown in the formula I; Cyclopentadienyl and alcoholic extract hydroxyl group with trifluoroethanol and the reaction of amido bridging aryloxy rare earth metal cyclopentadienyl title complex, take place proton exchange can take place in preparation method provided by the invention; Final trifluoroethanol and cyclopentadienyl generation substitution reaction; Generate final product suc as formula shown in the I,, nucleophilic substitution reaction takes place more easily because trifluoroethanol has stronger polarity; Make it to react with amido bridging aryloxy rare earth metal cyclopentadienyl compound; The product that obtains can improve the speed of ring-opening polymerization owing to had the existence of trifluoro ethoxy and rare earth metal, makes the required condition milder of reaction.
Description of drawings
The space structure figure of the product of Fig. 1 embodiment 3 preparations.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiments of the invention are described, but should be appreciated that these just restriction for further specifying feature and advantage of the present invention rather than patent of the present invention being required is described.
The invention provides a kind of amido bridging aryloxy rare earth metal alkoxide complexes, have the structure shown in the formula I:
Formula I
Wherein, Ln is a rare earth metal; R
1And R
2Be respectively hydrogen, methyl or the tertiary butyl.
Reality is trifluoro ethoxy with rare earth metal Cheng Jian's.So the compound shown in the formula I is preferably amido bridged linkage bis aryloxy rare earth metal trifluoro ethoxy compound, its general formula is: [ONNO] Ln (OCH
2CF
3) (THF); Wherein Ln is a rare earth metal, is selected from: a kind of in lanthanum, samarium, erbium, ytterbium or the yttrium; [ONNO] represents amido bridged linkage bis aryloxy part, [ONNO]=Me
2NCH
2CH
2N [CH
2-(2-O-C
6H
2-R
1-3-R
2-5)]
2, R
1And R
2Be selected from a kind of in hydrogen, methyl or the tertiary butyl respectively.
Owing to there is trifluoro ethoxy; And the coordination compound of amido bridged linkage bis aryloxy part and thulium formation; Simultaneously because the oxytropism of rare earth metal; In catalystsystem, the carbonyl in rac-beta-butyrolactone or the rac-rac-Lactide can with the rare earth metal coordination, cause corresponding chemical bond to be activated.The C-O key that links to each other with carbonyl with the attack of rare earth metal coordinate trifluoro ethoxy then causes the cyclic ester open loop, forms the rare earth alkoxylation compound of new chainpropagation.Repeat said process and form polymer chain.
Because amido bridging aryloxy rare earth metal title complex of the prior art is because the existence of amido bridged linkage bis aryloxy; Be to react with general alcohol; So, must provide a kind of method to obtain amido bridging aryloxy rare earth metal alkoxide complexes in order to obtain the compound shown in the formula I.
The preparation method of the compound shown in the formula I is specially:
A) title complex shown in the formula II is provided;
B) substitution reaction is taken place in title complex shown in the formula II and trifluoroethanol in solvent, obtain the compound shown in the formula I;
Formula II
Wherein, Ln is a rare earth metal; R
1And R
2Be respectively hydrogen, methyl or the tertiary butyl.
According to the present invention, the described compound of said formula II is preferably synthetic according to the method for bibliographical information, and the molecular formula of the title complex shown in the formula II is that [ONNO] LnCp (THF) is (referring to (a) Zhou Lanzhi University Of Suzhou master thesis 2007. (b) L.Z.Zhou; Y.M.Wang, Y.M.Yao, Y.Zhang; Q.Shen, J.Rare Earths, 2007; 25,544.);
The concrete following method of can also using prepares the compound shown in the formula II:
A1) with amido bridging bis-phenol shown in the formula III and tricyclopentadienyl rare earth compounding (C
5H
5)
3Ln (THF) is mixed with the title complex shown in the formula II.
Formula III
R wherein
1And R
2Be respectively hydrogen, methyl or the tertiary butyl.
Behind the title complex shown in the preparation formula II, preferably specifically operate as follows:
B 1) under the anhydrous and oxygen-free condition, title complex and the trifluoroethanol shown in the formula II is blended in the solvent for 1:1 ~ 1.05 in molar ratio, substitution reaction 10 ~ 20h takes place, remove said solvent, obtain crude product;
B2) with the said crude product of extracted in toluene, remove deposition, concentrated extract obtains crystal under 0 ~ 5 ℃, i.e. compound shown in the formula I.
According to the present invention; Title complex shown in the said formula II and trifluoroethanol are preferably 1:1 in molar ratio and are dissolved in aromatic solvent or the ether solvent and react 10 ~ 15h, and temperature of reaction is 10～90 ℃, more preferably 30 ~ 70 ℃; And be no more than the boiling point of solvent; Said temperature of reaction should not be low excessively, and it is very slow to be lower than 30 ℃ of reactions, and lower temperature causes reaction to be difficult to carry out.According to the present invention; Reactant ratio has very big influence to the overall process of reaction and the productive rate of product; The mol ratio of complex shown in the formula II and trifluoroethanol most preferably is 1:1～1.05; The trifluoroethanol consumption is few; Reaction not exclusively; Excessive meeting causes a lot of side reactions, and not only productive rate is low, and separates purification difficult;
According to the present invention, said reaction is preferably carried out under controlled atmosphere, and said rare gas element is argon gas or nitrogen.Because the very easily hydrolysis of compound shown in the formula I, so in the preparation process, preferably keep water-less environment.
Said step b1) factor that choice of Solvent need be considered described in comprises: solubility property, do not participate in the reaction and boiling point should not be too low; So said solvent is preferably aromatic solvent or ether solvent, said aromatic solvent is preferably: benzene or toluene, said ether solvent is preferably: THF, ether or glycol dimethyl ether.According to the present invention, shown in the following equation of total process of reaction: according to the present invention, the productive rate of the compound shown in the formula I of method preparation provided by the invention is 70%～80%.
The present invention requires to protect the application of above-mentioned amido bridged linkage bis aryloxy rare earth metal trifluoro ethoxy compound as catalysis rac-beta-butyrolactone polymeric single component catalyst simultaneously.
Using above-mentioned amido bridged linkage bis aryloxy rare earth metal trifluoro ethoxy title complex may further comprise the steps as the method for single component catalyst catalysis rac-beta-butyrolactone ring-opening polymerization:
With the title complex shown in the formula I and rac-beta-butyrolactone monomer is 1: 200～3000 to be blended in the solvent in molar ratio, obtains mixing solutions;
Ring-opening polymerization is taken place down at 10 ~ 70 ℃ in said mixing solutions, obtain gathering the rac-beta-butyrolactone.
Preparation process is specially: (1) is dissolved in the rac-beta-butyrolactone in the solvent under the inert atmosphere of anhydrous and oxygen-free, stirs down, and the solution that adds the title complex shown in the formula I carries out ring-opening polymerization;
(2) termination reaction uses precipitation agent to be settled out polymkeric substance, and drying obtains gathering the rac-beta-butyrolactone then.
According to the present invention, in the step (1), the temperature of reaction of ring-opening polymerization is preferably 10～70 ℃, and is no more than the boiling point of solvent; More preferably 20～40 ℃, and be no more than the boiling point of solvent; The mol ratio of rac-beta-butyrolactone and catalyzer is 200～3000: 1, and advantage of the present invention is that catalyst levels is few.Catalyst levels not only can reduce cost less, but also can reduce the residual quantity of metal ion neutralization product, improves the quality of product; The polymeric time is 10～120min; Said solvent is selected from: a kind of in toluene, benzene, methylene dichloride or the THF.
According to the present invention, the compound shown in the said formula I can directly be added in the polymerization system as catalyzer, but takes more convenient behind the wiring solution-forming.According to the present invention, the percent by volume of the methanol solution of hydrochloric acid is 4～6% in the said step (2).If no special instructions, all other chemical feedstockss are the commercial goods.
Because the technique scheme utilization, the present invention compared with prior art has advantage:
1. amido bridged linkage bis aryloxy rare earth metal trifluoro ethoxy compound according to the invention is synthetic convenient, separates and purifies conveniently, and structure is clear and definite, and yield is high.
2. amido bridged linkage bis aryloxy rare earth metal trifluoro ethoxy compound according to the invention is active high as the ring-opening polymerization of catalyst rac-beta-butyrolactone, and rac-beta-butyrolactone and catalyst molar ratio reach as high as 3000:1; The controllability of catalyst rac-beta-butyrolactone ring-opening polymerization and selectivity are also fine in addition, obtain HMW, narrow molecular weight distributions between rule gather beta-butyrolactone.
The present invention requires to protect the application of above-mentioned amido bridged linkage bis aryloxy rare earth metal alkoxy compound as catalysis rac-rac-Lactide polymeric single component catalyst simultaneously.
Using above-mentioned amido bridged linkage bis aryloxy rare earth metal alkoxide complexes may further comprise the steps as the method for single component catalyst catalysis rac-rac-Lactide ring-opening polymerization:
With the said title complex of formula I and rac-lactide monomer is 1: 200～3000 to be blended in the solvent in molar ratio, obtains mixing solutions;
Ring-opening polymerization is taken place down at 10 ~ 40 ℃ in said mixing solutions, obtain gathering the rac-rac-Lactide.
Preparation process is specially: (1) is dissolved in the rac-rac-Lactide in the solvent under the inert atmosphere of anhydrous and oxygen-free, stirs down, adds the solution of the title complex shown in the formula I;
(2) termination reaction uses precipitation agent to be settled out polymkeric substance, and drying obtains gathering the rac-rac-Lactide then.
According to the present invention; In the said step (1), the temperature of reaction of ring-opening polymerization is preferably 10～40 ℃, and more preferably temperature is 20～25 ℃; The mol ratio of the title complex shown in rac-rac-Lactide and the formula I is 200～3000: 1, and advantage of the present invention is that catalyst activity height and selectivity are good.The polymeric time is 10～120min; Said solvent is selected from: a kind of in toluene, benzene, methylene dichloride or the THF.
According to the present invention, the title complex shown in the formula I can directly be added in the polymerization system as catalyzer, but takes more convenient behind the wiring solution-forming.The solvent of catalyst solution is toluene, benzene, methylene dichloride or THF.According to the present invention, the percent by volume of the methanol solution of hydrochloric acid is 4～6% in the step (2).If no special instructions, all other chemical feedstockss are the commercial goods.
Because the technique scheme utilization, the present invention compared with prior art has advantage:
1. amido bridged linkage bis aryloxy rare earth metal alkoxide complexes according to the invention is synthetic convenient, and yield is high.
2. amido bridged linkage bis aryloxy rare earth metal alkoxide complexes according to the invention is active high as catalyst rac-rac-Lactide or the ring-opening polymerization of rac-beta-butyrolactone; Rac-rac-Lactide and catalyst molar ratio reach as high as 3000:1, and rac-beta-butyrolactone and catalyst molar ratio reach as high as 3000:1; The selectivity of catalyst rac-rac-Lactide or the ring-opening polymerization of rac-beta-butyrolactone is also fine in addition, and the gained polylactide is all the master with assorted, and gathering GBL is main with a rule.
Below be the specific embodiment of the invention, introduce technical scheme of the present invention and excellent experiment effect in detail.Wherein Cp is a cyclopentadienyl; H
2L is amido bridged bis-phenol; Bu
tBe the tertiary butyl.
Embodiment 1
Preparation [ONNO] YCp (THF) (R
1=R
2=Bu
t)
Under 25 ℃, with 3.05 mmole H
2The tetrahydrofuran solution of L joins and contains Cp
3The tetrahydrofuran solution of Y (THF) (3.05 mmole) behind the reaction 1h, is taken out and is desolvated, and adds 20 ml n-hexanes and adds extraction heat, and centrifugal, clear liquid shifts, and 25 ℃ of following hold over night are separated out clear crystal 2.06 grams (2.14 mmole), productive rate 70%.
Obtain ultimate analysis through detection: C, 68.59; H, 9.00; N, 3.82; Y, 11.45.
1HNMR (300MHz, C
6D
6, 25 ° of C): δ 7.60 (s, 2H, ArH), 7.09 (s, 2H, ArH), 6.62 (s, 5H, C
5H
5), 3.72 (d,
2J (H, H)=12.2Hz, 4H, ArCH
2N), 3.49 (br, 4H, α-CH
2THF), 2.73 (d,
2J (H, H)=12.9Hz, 4H, N (CH
2)
2N), 1.83 (s, 18H, C (CH
3)
3), 1.65 (br, 6H, N (CH
3)
2), 1.45 (s, 18H, C (CH
3)
3), 1.02 (br, 4H, β-CH
2THF).
13C{1H}NMR (101MHz, C
6D
6, 25 ° of C): δ 162.7,136.5,136.2,125.6,124.7,124.2 (Ar-C), 110.7 (C
5H
5), 71.1 (α-CH
2THF), 66.5 (ArCH
2N), 60.0 (N (CH
2)
2N), 49.2 (N (CH
3)
2), 35.6 (C (CH
3)
3), 34.1 (C (CH
3)
3), 32.3 (C (CH
3)
3), 30.2 (C (CH
3)
3), 24.9 (β-CH
2THF).Infrared absorption spectrum data: 2955s, 2909s, 1605s, 1443w, 1335s, 1250s, 1026s, 864s, 818m, 756m, 509m, above digital proof compound success.
Embodiment 2
Preparation [ONNO] LaCp (THF) (R
1=R
2=Bu
t)
Under 25 ℃, with 2.24 mmole H
2The tetrahydrofuran solution of L joins and contains Cp
3The tetrahydrofuran solution of La (THF) (2.24 mmole) behind the reaction 1h, is taken out and is desolvated, and adds 25 ml n-hexanes and adds extraction heat, and centrifugal, clear liquid shifts, and 25 ℃ of following hold over night are separated out clear crystal 1.18 grams (1.66 mmole), productive rate 74%.Decomposition temperature: 196-198 ° C.
Ultimate analysis: C, 62.34; H, 7.43; N, 3.72; La, 19.57.C
37H
55LaN
2O
3(714.74) theoretical value: C, 62.18; H, 7.76; N, 3.92; La, 19.43);
1HNMR (δ, ppm, CDCl
3): 7.03 (s, 2H, Ph), 6.97 (s, 2H, Ph), 6.41 (s, 5H, C
5H
5), 3.91 (s, 4H, THF), 3.82 ~ 3.79 (d, 4H, NCH
2Ph), 2.89 ~ 2.99 (m, 4H, NCH
2CH
2N), 2.04 (s, 6H, NCH
3), 1.92 (s, 6H, ArCH
3), 1.81 (s, 4H, THF), 1.55 (s, 18H, C (CH
3)
3); Infrared absorption spectrum data: 2952s, 2910s, 1605s, 1448w, 1335s, 1256s, 1026s, 864s, 815m, 756m, 513m.Above digital proof compound success.
Embodiment 3
Preparation [ONNO] Y (OCH
2CF
3) (THF).
Under 25 ℃, with 6.76 mmole H
2The tetrahydrofuran solution of L joins and contains Cp
3The tetrahydrofuran solution of Y (THF) (6.76 mmole), behind the reaction 1h, the tetrahydrofuran solution with 6.76 mmole trifluoroethanols joins in the above-mentioned reaction solution again, and 60 ℃ are continued stirring reaction 12h.
Take out and desolvate, add 20 milliliters of toluene and add extraction heat, centrifugal, clear liquid shifts, and 25 ℃ of following hold over night are separated out clear crystal 3.70 grams (4.73 mmole), productive rate 70%.
Ultimate analysis: C, 60.59; H, 8.43; N, 3.73; Y, 11.26.
1H NMR (300MHz, C
6D
6, 25 ° of C): δ 7.57 (s, 2H, ArH), 7.10 (d, 2H, J (H, H)=11.7Hz, ArH), 4.35 (s, 2H, OCH
2CF
3), 3.94 (br, 2H, ArCH
2N), 3.85 (br, 4H, α-CH
2THF), 2.89 (br, 2H, ArCH
2N), 2.26 (br, 2H, N (CH
2)
2N), 1.71 (s, 18H, C (CH
3)
3), 1.66 (br, 6H, N (CH
3)
2), 1.53 (br, 2H, N (CH
2)
2N), 1.43 (s, 18H, C (CH
3)
3), 1.26 (br, 4H, β-CH
2THF).
13C{1H}NMR (101MHz, C
6D
6, 25 ° of C): δ 161.8,136.5,136.4,125.8,124.6,124.5 (Ar-C), 70.7 (α-CH
2THF), 66.6 (CF
3), 65.2 (CH
2CF
3), 58.8 (ArCH
2N), 48.9 (N (CH
2)
2N), 45.6 (N (CH
3)
2), 35.5 (C (CH
3)
2), 34.3 (C (CH
3)
3), 32.3 (C (CH
3)
3), 30.4 (C (CH
3)
3), 25.3 (β-CH
2THF).Infrared absorption spectrum data: 2951s, 2905m, 2867m, 1608w, 1473s, 1282m, 1245w, 1192m, 1153m, 1028m, 995w, 958m, 922w, 877m, 833m, 776w, 739m, above digital proof compound success.
Embodiment 4
Preparation [ONNO] Yb (OCH
2CF
3) (THF).
Under 25 ℃, with 4.86 mmole H
2The tetrahydrofuran solution of L joins and contains Cp
3The tetrahydrofuran solution of Yb (THF) (4.86 mmole), behind the reaction 1h, the tetrahydrofuran solution with 4.86 mmole trifluoroethanols joins in the above-mentioned reaction solution again, and 60 ℃ are continued stirring reaction 12h.
Take out and desolvate, add 20 milliliters of toluene and add extraction heat, centrifugal, clear liquid shifts, and 25 ℃ of following hold over night are separated out clear crystal 3.29 grams (3.79 mmole), productive rate 71%.
Ultimate analysis: C, 55.44; H, 7.56; N, 3.37; Yb, 19.83.Yb, 19.96); Infrared absorption spectrum data: 2956s, 2904m, 2865m, 1604w, 1472s, 1281m, 1243w, 1192m, 1154m, 1026m, 991w, 960m, 922w, 880m, 838m, 778w, 744m, above digital proof compound success.
Embodiment 5
Preparation [ONNO] Er (OCH
2CF
3) (THF).
Under 25 ℃, with 2.29 mmole H
2The tetrahydrofuran solution of L joins and contains Cp
3The tetrahydrofuran solution of Er (THF) (2.29 mmole), behind the reaction 1h, the tetrahydrofuran solution with 2.29 mmole trifluoroethanols joins in the above-mentioned reaction solution again, and 60 ℃ are continued stirring reaction 12h.
Take out and desolvate, add 15 milliliters of toluene and add extraction heat, centrifugal, clear liquid shifts, and 25 ℃ of following hold over night are separated out clear crystal 1.32 grams (1.53 mmole), productive rate 67%.
Ultimate analysis: C, 56.51; H, 7.57; N, 3.49; Er, 19.56. infrared absorption spectrum data: 2954s, 2904m, 2867m, 1608w, 1473s, 1281m, 1246w, 1192m, 1153m, 1026m, 991w, 960m, 922w, 879m, 833m, 775w, 740m, above digital proof compound success.
Embodiment 6
[ONNO] Y (OCH
2CF
3) (THF) catalysis rac-beta-butyrolactone ring-opening polymerization.
In the reaction flask of handling through dehydration and deoxidation, under argon shield, add rac-beta-butyrolactone 0.38 gram (4.42 mmole), add 0.71 milliliter of toluene, behind 25 ℃ of stirring 5min, add catalyzer 1.15 milliliter (9.6 * 10
-3Mmole), 25 ℃ of polymerization 10min are with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, must gather GBL 0.36 to constant weight after the vacuum-drying and restrain productive rate 95%.The theoretical molecular of polymkeric substance is 3.27 ten thousand [M
n(calcd)=86 * 400 * 95%], GPC actual measurement number-average molecular weight (M
n) be 4.91 ten thousand, MWD (M
w/ M
n) be 1.29, a rule content is 83%.
Embodiment 7
[ONNO] Y (OCH
2CF
3) (THF) catalysis rac-beta-butyrolactone ring-opening polymerization
In the reaction flask of handling through dehydration and deoxidation, under argon shield, add rac-beta-butyrolactone 0.49 gram (5.70 mmole), add 2.26 milliliters of toluene, behind 25 ℃ of stirring 5min, add catalyzer 0.59 milliliter (9.6 * 10
-3Mmole), 25 ℃ of polymerization 10min are with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, must gather GBL 0.36 to constant weight after the vacuum-drying and restrain productive rate 80%.The theoretical molecular of polymkeric substance is 6.88 ten thousand [M
n(calcd)=86 * 1000 * 80%], GPC actual measurement number-average molecular weight (M
n) be 8.64 ten thousand, MWD (M
w/ M
n) be 1.37, a rule content is 82%.
Embodiment 8
[ONNO] Yb (OCH
2CF
3) (THF) catalysis rac-beta-butyrolactone ring-opening polymerization
In the reaction flask of handling through dehydration and deoxidation, under argon shield, add rac-beta-butyrolactone 0.58 gram (6.74 mmole), add 2.26 milliliters of toluene, behind 25 ℃ of stirring 5min, add catalyzer 2.16 milliliter (9.3 * 10
-3Mmole), 25 ℃ of polymerization 10min are with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, must gather GBL 0.55 to constant weight after the vacuum-drying and restrain productive rate 94%.The theoretical molecular of polymkeric substance is 4.85 ten thousand [M
n(calcd)=86 * 600 * 94%], GPC actual measurement number-average molecular weight (M
n) be 6.08 ten thousand, MWD (M
w/ M
n) be 1.19, a rule content is 84%.
Embodiment 9
[ONNO] Yb (OCH
2CF
3) (THF) catalysis rac-beta-butyrolactone ring-opening polymerization
In the reaction flask of handling through dehydration and deoxidation, under argon shield, add rac-beta-butyrolactone 0.38 gram (4.42 mmole), add 1.02 milliliters of toluene, behind 25 ℃ of stirring 5min, add catalyzer 1.19 milliliter (9.3 * 10
-3The mmole milliliter
-1), 25 ℃ of polymerization 10min are with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, must gather GBL 0.37 to constant weight after the vacuum-drying and restrain productive rate 97%.The theoretical molecular of polymkeric substance is 3.34 ten thousand [M
n(calcd)=86 * 400 * 97%], GPC actual measurement number-average molecular weight (M
n) be 3.58 ten thousand, MWD (M
w/ M
n) be 1.22, a rule content is 83%.
Embodiment 10
[ONNO] Er (OCH
2CF
3) (THF) catalysis rac-beta-butyrolactone ring-opening polymerization
In the reaction flask of handling through dehydration and deoxidation, under argon shield, add rac-beta-butyrolactone 0.37 gram (4.30 mmole), add 0.93 milliliter of toluene, behind 25 ℃ of stirring 5min, add catalyzer 1.22 milliliter (8.8 * 10
-3The mmole milliliter
-1), 25 ℃ of polymerization 5min are with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, must gather GBL 0.35 to constant weight after the vacuum-drying and restrain productive rate 94%.The theoretical molecular of polymkeric substance is 3.23 ten thousand [M
n(calcd)=86 * 400 * 94%], GPC actual measurement number-average molecular weight (M
n) be 3.64 ten thousand, MWD (M
w/ M
n) be 1.31, a rule content is 83%.
Embodiment 11
(THF) catalysis rac-beta-butyrolactone ring-opening polymerization of [ONNO] Er (OCH2CF3)
In the reaction flask of handling through dehydration and deoxidation, under argon shield, add rac-beta-butyrolactone 0.55 gram (6.40 mmole), add 2.00 milliliters of toluene, behind 25 ℃ of stirring 5min, add catalyzer 1.20 milliliter (8.8 * 10
-3The mmole milliliter
-1), 25 ℃ of polymerization 10min are with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, must gather GBL 0.52 to constant weight after the vacuum-drying and restrain productive rate 94%.The theoretical molecular of polymkeric substance is 4.85 ten thousand [M
n(calcd)=86 * 600 * 94%], GPC actual measurement number-average molecular weight (M
n) be 4.68 ten thousand, MWD (M
w/ M
n) be 1.26, a rule content is 82%.
Embodiment 12
[ONNO] Y (OCH
2CF
3) (THF) catalysis rac-rac-Lactide ring-opening polymerization
In the reaction flask of handling through dehydration and deoxidation, under argon shield, add rac-rac-Lactide 0.32 gram (2.22 mmole), add 1.59 milliliters of THFs, behind 25 ℃ of stirring 5min, add catalyzer 0.62 milliliter (8.9 * 10
-3Mmole), 25 ℃ of polymerization 1h are with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, gets polylactide 0.31 to constant weight after the vacuum-drying and restrains productive rate 98%.
Adopt routine techniques to survey the molecular weight of polymkeric substance, specifically may further comprise the steps: polymkeric substance is made into the tetrahydrofuran solution of desired concn, determining molecular weight and MWD on the PL-50 type gel permeation chromatograph that PL company produces.Test condition: 40 ℃ of temperature, THF is made eluent, 1.0 milliliters/min of leacheate flow velocity.The theoretical molecular of polymkeric substance is 5.64 ten thousand [M
n(calcd)=144 * 400 * 98%], GPC actual measurement number-average molecular weight (M
n) be 5.78 ten thousand, MWD (M
w/ M
n) be 1.06, assorted is 99% with content.
Embodiment 13
[ONNO] Yb (OCH
2CF
3) (THF) catalysis rac-rac-Lactide ring-opening polymerization
In the reaction flask of handling through dehydration and deoxidation, under argon shield, add rac-rac-Lactide 0.60 gram (4.18 mmole), add 1.59 milliliters of THFs, behind 25 ℃ of stirring 5min, add catalyzer 0.32 milliliter (8.6 * 10
-3Mmole), 25 ℃ of polymerization 1h are with the alcohol termination reaction that contains 5% hydrochloric acid;
Polymkeric substance is used industrial alcohol precipitation, gets polylactide 0.50 to constant weight after the vacuum-drying and restrains productive rate 84%.
Adopt routine techniques to survey the molecular weight of polymkeric substance, specifically may further comprise the steps: polymkeric substance is made into the tetrahydrofuran solution of desired concn, determining molecular weight and MWD on the PL-50 type gel permeation chromatograph that PL company produces.Test condition: 40 ℃ of temperature, THF is made eluent, 1.0 milliliters/min of leacheate flow velocity.The theoretical molecular of polymkeric substance is 18.14 ten thousand [M
n(calcd)=144 * 1500 * 84%], GPC actual measurement number-average molecular weight (M
n) be 16.96 ten thousand, MWD (M
w/ M
n) be 1.05, assorted is 99% with content.
Through above embodiment, can prove that amido bridged linkage bis aryloxy rare earth metal trifluoro ethoxy title complex 1. according to the invention is synthetic convenient, yield is high.2. amido bridged linkage bis aryloxy rare earth metal trifluoro ethoxy title complex according to the invention is active high as catalyst rac-rac-Lactide or the ring-opening polymerization of rac-beta-butyrolactone, and rac-rac-Lactide and rac-beta-butyrolactone and catalyst molar ratio reach as high as 3000:1; The selectivity of catalyst rac-rac-Lactide or the ring-opening polymerization of rac-beta-butyrolactone is also fine in addition, and the gained polylactide is all the master with assorted, and gathering GBL is main with a rule.
More than detailed introduction has been carried out in a kind of amido bridged linkage bis aryloxy rare earth metal trifluoro ethoxy title complex provided by the invention and preparation thereof and application; Having used concrete example among this paper sets forth principle of the present invention and embodiment; The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. the title complex shown in the formula I,
Formula I
Wherein, Ln is a rare earth metal; R
1And R
2Be respectively hydrogen, methyl or the tertiary butyl.
2. title complex according to claim 1 is characterized in that, said Ln is lanthanum, samarium, erbium, ytterbium or yttrium.
3. the preparation method of the described title complex of claim 1 is characterized in that, comprising:
A) title complex shown in the formula II is provided;
B) substitution reaction is taken place in title complex shown in the formula II and trifluoroethanol in solvent, obtain the compound shown in the formula I;
Formula II
Wherein, Ln is a rare earth metal; R
1And R
2Be respectively hydrogen, methyl or the tertiary butyl.
4. preparation method according to claim 3 is characterized in that step a) is specially:
A1) with amido bridging bis-phenol shown in the formula III and tricyclopentadienyl rare earth compounding (C
5H
5)
3Ln (THF) is mixed with the title complex shown in the formula II;
Formula III
Wherein, R
1And R
2Be respectively hydrogen, methyl or the tertiary butyl.
5. preparation method according to claim 3 is characterized in that, said Ln is lanthanum, samarium, erbium, ytterbium or yttrium.
6. preparation method according to claim 3 is characterized in that step b) is specially:
B1) under anhydrous and oxygen-free, title complex and the trifluoroethanol shown in the formula II is blended in the solvent for 1:1 ~ 1.05 in molar ratio, substitution reaction 10 ~ 20h takes place, remove said solvent, obtain crude product;
B2) with the said crude product of extracted in toluene, remove deposition, concentrated extract obtains crystal under 0 ~ 5 ℃, i.e. compound shown in the formula I.
7. according to claim 3 or 6 described preparing methods, it is characterized in that said solvent is aromatic solvents or ether solvent.
8. preparation method according to claim 3 is characterized in that, the temperature of substitution reaction described in the step b) is 10 ~ 90 ℃.
9. a preparation method who gathers the rac-beta-butyrolactone is characterized in that, comprising:
With the described title complex of claim 1 and rac-beta-butyrolactone monomer is 1: 200～3000 to be blended in the solvent in molar ratio, obtains mixing solutions;
Ring-opening polymerization is taken place down at 10 ~ 70 ℃ in said mixing solutions, obtain gathering the rac-beta-butyrolactone.
10. a preparation method who gathers the rac-rac-Lactide is characterized in that, comprising:
With the described title complex of claim 1 and rac-lactide monomer is 1: 200～3000 to be blended in the solvent in molar ratio, obtains mixing solutions;
Ring-opening polymerization is taken place down at 10 ~ 40 ℃ in said mixing solutions, obtain gathering the rac-rac-Lactide.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103483362A (en) * | 2013-09-04 | 2014-01-01 | 苏州大学 | Amido-bridged bisaryloxy rare-earth metal guanidyl compound as well as preparation method and application of same |
| CN107573490A (en) * | 2017-09-07 | 2018-01-12 | 苏州大学 | The method for preparing L lactides and ε caprolactone random copolymers |
| CN112062944A (en) * | 2020-09-21 | 2020-12-11 | 安徽英特力工业工程技术有限公司 | Lactide ring-opening polymerization catalyst composition and preparation method thereof |
| CN115612081A (en) * | 2022-10-25 | 2023-01-17 | 苏州大学 | Preparation method of cyclic poly (L-lactide) |
| CN115746029A (en) * | 2022-10-25 | 2023-03-07 | 苏州大学 | Benzoxazine functionalized amino-bridged polyaryloxy rare earth metal complex and preparation method and catalytic application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483362A (en) * | 2013-09-04 | 2014-01-01 | 苏州大学 | Amido-bridged bisaryloxy rare-earth metal guanidyl compound as well as preparation method and application of same |
| CN103483362B (en) * | 2013-09-04 | 2016-01-20 | 苏州大学 | Amido bridged linkage bis aryloxy rare earth metal guanidine compound and its preparation method and application |
| CN107573490A (en) * | 2017-09-07 | 2018-01-12 | 苏州大学 | The method for preparing L lactides and ε caprolactone random copolymers |
| CN112062944A (en) * | 2020-09-21 | 2020-12-11 | 安徽英特力工业工程技术有限公司 | Lactide ring-opening polymerization catalyst composition and preparation method thereof |
| CN115612081A (en) * | 2022-10-25 | 2023-01-17 | 苏州大学 | Preparation method of cyclic poly (L-lactide) |
| CN115746029A (en) * | 2022-10-25 | 2023-03-07 | 苏州大学 | Benzoxazine functionalized amino-bridged polyaryloxy rare earth metal complex and preparation method and catalytic application thereof |
| CN115612081B (en) * | 2022-10-25 | 2023-05-12 | 苏州大学 | Preparation method of cyclic poly (L-lactide) |
| CN115746029B (en) * | 2022-10-25 | 2024-05-31 | 苏州大学 | Benzoxazine functionalized amino bridged poly aryloxy rare earth metal complex, preparation method and catalytic application thereof |
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