CN102702241B - 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
- Publication number
- CN102702241B CN102702241B CN201210170636.1A CN201210170636A CN102702241B CN 102702241 B CN102702241 B CN 102702241B CN 201210170636 A CN201210170636 A CN 201210170636A CN 102702241 B CN102702241 B CN 102702241B
- Authority
- CN
- China
- Prior art keywords
- rac
- formula
- preparation
- title complex
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention provides complexes shown in formula I, wherein Ln is rare earth metal; and R<1> and R<2> 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 organometallics preparation field, be specifically related to a kind of amido bridged linkage bis aryloxy rare earth metal trifluoro ethoxy title complex and Synthesis and applications thereof.
Background technology
Because rare earth metal alkoxide complexes can catalysis cyclic ester monomers ring-opening polymerization effectively, and have good controllability, therefore the synthesis of rare earth metal alkoxide complexes and catalytic performance research thereof cause people's interest widely.
2003, Carpentier seminar investigated with regard to the catalytic performance starting offside arm straps methoxyl group amido bridged linkage bis aryloxy rare earth compound.They find that corresponding aminate can cause the ring-opening polymerization of meso-lactide, and under the condition that there is Virahol, they can be polymerized with the controlled stereoselectivity of beta-butyrolactone by high reactivity ground catalysis rac-rac-Lactide, gained polylactide is high heterotactic polymer, poly-butyrolactone based on syndiotactic (see (a) A.Amgoune, C.M.Thomas, S.Ilinca, 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.Thomasand J.F.Carpentier, Macromol.Rapid Commun., 2007,28,693.).
2007, Cui Dong plum seminar utilized trialkyl rare earth compound and amido bridging bis-phenol generation alkyl eliminative reaction, has synthesized corresponding rare earth metal trimethyl silicane methyl compound.These rare earth trimethyl silicane methyl compound polymerizations to rac-lactide show good catalytic activity, obtain high assorted with polymkeric substance, but in catalyst system, add alcohol make catalyzer lose activity (see 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 plum group reports bridged linkage bis aryloxy rare earth trimethyl silicane methyl compound can cause rac-Lactide polymerization under trolamine existent condition, obtain having the star polylactide of three-arm arrangement (see W.Zhao, D.M.Cui and X.S.Chen.Macromolecules 2010,43,6678).
2009, Coates seminar, by amido bridged linkage bis aryloxy yttrium aminate and isopropanol reaction, obtained first amido bridged linkage bis aryloxy yttrium isopropoxy compound through structural characterization, find its can the syndiotactic polymerization of catalysis beta-butyrolactone effectively (see 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; comprise benzyloxy compound, isopropoxy compound and methoxy compound etc.; can be standby by the exchange system of carbon bridged linkage bis aryloxy rare earth metal cyclopentadienyl compound and alcohol, the method raw material is cheaply easy to get, and product separation purification is simple and convenient (see (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, corresponding amido bridged linkage bis aryloxy rare earth metal alkoxide complexes is not prepared (see L.Z.Zhou, Y.M.Wang, Y.M.Yao by this kind of method, Y.Zhang, Q.Shen, J.Rare Earths, 2007,25,544.).
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of catalytic activity higher and amido bridged linkage bis aryloxy rare earth metal trifluoro ethoxy title complex of easily preparation and preparation method thereof, and its application in catalyzed preparation of poly rac-beta-butyrolactone and poly-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 rare earth metal; R
1and R
2be respectively hydrogen, methyl or the tertiary butyl.
Preferably, described Ln is lanthanum, samarium, erbium, ytterbium or yttrium.
Present invention also offers the preparation method of the title complex described in a kind of formula I, comprising:
A) title complex shown in formula II is provided;
B) be there is substitution reaction in a solvent in the title complex shown in formula II and trifluoroethanol, obtain the compound shown in formula I;
Formula II
Wherein, Ln is rare earth metal; R
1and R
2be respectively hydrogen, methyl or the tertiary butyl.
Preferably, step a) is specially:
A1) by the amido bridging bis-phenol shown in formula III and tricyclopentadienyl rare earth compounding (C
5h
5)
3ln(THF) title complex shown in formula II is mixed with;
Formula III
Wherein, R
1and R
2be respectively hydrogen, methyl or the tertiary butyl.
Preferably, described Ln is lanthanum, samarium, erbium, ytterbium or yttrium.
Preferably, step b) is specially:
B1) under anhydrous and oxygen-free condition, the title complex shown in formula II is mixed in a solvent for 1:1 ~ 1.05 with trifluoroethanol in molar ratio, substitution reaction 10 ~ 20h occurs, removes described solvent, obtain crude product;
B2) extract described crude product with toluene, removing precipitation, concentrated extract, obtains crystal at 0 ~ 5 DEG C, the compound namely shown in formula I.
Preferably, described solvent is aromatic solvents or ether solvent.
Preferably, the temperature of substitution reaction described in step b) is 40 ~ 60 DEG C.
Present invention also offers a kind of preparation method of poly-rac-beta-butyrolactone, comprising:
Be 1: 200 ~ 3000 mix in a solvent in molar ratio by the title complex shown in formula I and rac-beta-butyrolactone monomer, obtain mixing solutions;
At 10 ~ 70 DEG C, be there is ring-opening polymerization in described mixing solutions, obtain poly-rac-beta-butyrolactone.
Present invention also offers a kind of preparation method of poly-rac-rac-Lactide, comprising:
Be 1: 200 ~ 3000 mix in a solvent in molar ratio by title complex described in formula I and rac-lactide monomer, obtain mixing solutions;
At 10 ~ 40 DEG C, be there is ring-opening polymerization in described mixing solutions, obtain poly-rac-rac-Lactide.
Compound provided by the invention, shown in I, owing to being amido bridged linkage bis aryloxy rare earth metal trifluoro ethoxy title complex, due to the existence of amido bridge ligand, rare earth metal and alkoxyl group, makes it higher in the catalytic activity of catalyzed ring opening polymerization reaction.
Present invention also offers the preparation method of the compound shown in a kind of formula I, title complex a) provided shown in formula II is provided, b) be there is substitution reaction in a solvent in the title complex shown in formula II and trifluoroethanol, obtain the compound shown in formula I, preparation method provided by the invention, trifluoroethanol and amido bridging aryloxy rare earth metal cyclopentadienyl title complex are reacted, can proton exchange be there is in generation cyclopentadienyl and alcoholic extract hydroxyl group, final trifluoroethanol and cyclopentadienyl generation substitution reaction, generate final product such as formula shown in I, because trifluoroethanol has stronger polarity, more easily there is nucleophilic substitution reaction, it can be reacted with amido bridging aryloxy rare earth metal cyclopentadienyl compound, the product obtained is owing to being provided with the existence of trifluoro ethoxy and rare earth metal, the speed of ring-opening polymerization can be improved, make the condition milder needed for reaction.
Accompanying drawing explanation
The space structure figure of product prepared by Fig. 1 embodiment 3.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these describe just as further illustrating the features and advantages of the present invention instead of the restriction to patent requirements of the present invention.
The invention provides a kind of amido bridging aryloxy rare earth metal alkoxide complexes, there is the structure shown in formula I:
Formula I
Wherein, Ln is 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 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 rare earth metal, is selected from: the one in lanthanum, samarium, erbium, ytterbium or 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 the one 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 due to the oxytropism of rare earth metal, in catalyst system, carbonyl in rac-beta-butyrolactone or rac-rac-Lactide can with rare earth metal coordination, cause corresponding chemical bond to be activated.Then the C-O key be connected with carbonyl with the trifluoro ethoxy attack of rare earth metal coordination, causes 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 complex of the prior art is due to the existence of amido bridged linkage bis aryloxy, can not carry out reacting with general alcohol, so in order to obtain the compound shown in formula I, a kind of method must be provided to obtain amido bridging aryloxy rare earth metal alkoxide complexes.
The preparation method of the compound shown in formula I is specially:
A) title complex shown in formula II is provided;
B) be there is substitution reaction in a solvent in the title complex shown in formula II and trifluoroethanol, obtain the compound shown in formula I;
Formula II
Wherein, Ln is rare earth metal; R
1and R
2be respectively hydrogen, methyl or the tertiary butyl.
According to the present invention, compound described in described formula II preferably synthesizes according to the method for bibliographical information, the molecular formula of the title complex shown in formula II is that [ONNO] LnCp (THF) is (see (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 compound that can also make with the following method shown in preparation formula II:
A1) by the amido bridging bis-phenol shown in formula III and tricyclopentadienyl rare earth compounding (C
5h
5)
3ln(THF) title complex shown in formula II is mixed with.
Formula III
Wherein R
1and R
2be respectively hydrogen, methyl or the tertiary butyl.
After title complex shown in preparation formula II, preferably specifically proceed as follows:
B 1) under anhydrous and oxygen-free condition, the title complex shown in formula II is mixed in a solvent for 1:1 ~ 1.05 with trifluoroethanol in molar ratio, there is substitution reaction 10 ~ 20h, remove described solvent, obtain crude product;
B2) extract described crude product with toluene, removing precipitation, concentrated extract, obtains crystal at 0 ~ 5 DEG C, the compound namely shown in formula I.
According to the present invention, title complex shown in described formula II and trifluoroethanol are preferably 1:1 in molar ratio and are dissolved in aromatic solvent or ether solvent and react 10 ~ 15h, temperature of reaction is 10 ~ 90 DEG C, be more preferably 30 ~ 70 DEG C, and be no more than the boiling point of solvent, described temperature of reaction is unsuitable too low, and very slow lower than 30 DEG C of reactions, lower temperature causes reaction to be difficult to carry out.According to the present invention, reactant ratio has a significant impact the whole process of reaction and the productive rate of product, the mol ratio of the title complex shown in formula II and trifluoroethanol most preferably is 1:1 ~ 1.05, trifluoroethanol consumption is few, reaction not exclusively, excessive meeting causes a lot of side reaction, and not only productive rate is low, and separating-purifying difficulty;
According to the present invention, described reaction is preferably carried out under controlled atmosphere, and described rare gas element is argon gas or nitrogen.Because the compound shown in formula I is very easily hydrolyzed, so preferably keep water-less environment in preparation process.
Described step b1) described in solvent selection need consider factor comprise: solubility property, do not participate in reaction and boiling point should not be too low; So described solvent is preferably aromatic solvent or ether solvent, described aromatic solvent is preferably: benzene or toluene, and described ether solvent is preferably: tetrahydrofuran (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 formula I prepared by method provided by the invention is 70% ~ 80%.
The application of the single component catalyst that claimed above-mentioned amido bridged linkage bis aryloxy rare earth metal trifluoro ethoxy compound is polymerized as catalysis rac-beta-butyrolactone while of the present invention.
Apply above-mentioned amido bridged linkage bis aryloxy rare earth metal trifluoro ethoxy title complex to comprise the following steps as the method for single component catalyst catalysis rac-beta-butyrolactone ring-opening polymerization:
Be 1: 200 ~ 3000 mix in a solvent in molar ratio by the title complex shown in formula I and rac-beta-butyrolactone monomer, obtain mixing solutions;
At 10 ~ 70 DEG C, be there is ring-opening polymerization in described mixing solutions, obtain poly-rac-beta-butyrolactone.
Preparation process is specially: rac-beta-butyrolactone, under the inert atmosphere of anhydrous and oxygen-free, is dissolved in solvent by (1), and under stirring, the solution adding the title complex shown in formula I carries out ring-opening polymerization;
(2) termination reaction, use precipitation agent to be settled out polymkeric substance, then drying obtains poly-rac-beta-butyrolactone.
According to the present invention, in step (1), the temperature of reaction of ring-opening polymerization is preferably 10 ~ 70 DEG C, and is no more than the boiling point of solvent; Be more preferably 20 ~ 40 DEG C, 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 costs less, but also can reduce the residual quantity of metal ion neutralization product, improves the quality of product; The time of polymerization is 10 ~ 120min; Described solvent is selected from: the one in toluene, benzene, methylene dichloride or tetrahydrofuran (THF).
According to the present invention, the compound shown in described formula I, as catalyzer, can directly be added in polymerization system, but takes more convenient after wiring solution-forming.According to the present invention, in described step (2), the percent by volume of the methanol solution of hydrochloric acid is 4 ~ 6%.If no special instructions, other chemical feedstockss all are commercial goods.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. amido bridged linkage bis aryloxy rare earth metal trifluoro ethoxy compound synthesis of the present invention is convenient, and separating-purifying is convenient, and structure is clear and definite, and yield is high.
2. amido bridged linkage bis aryloxy rare earth metal trifluoro ethoxy compound of the present invention is high as the activity of catalyst rac-beta-butyrolactone ring-opening polymerization, 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 the poly-beta-butyrolactone of rule between high molecular, narrow molecular weight distributions.
The application of the single component catalyst that claimed above-mentioned amido bridged linkage bis aryloxy rare earth metal alkoxy compound is polymerized as catalysis rac-rac-Lactide while of the present invention.
Apply above-mentioned amido bridged linkage bis aryloxy rare earth metal alkoxide complexes to comprise the following steps as the method for single component catalyst catalysis rac-rac-Lactide ring-opening polymerization:
Be 1: 200 ~ 3000 mix in a solvent in molar ratio by title complex described in formula I and rac-lactide monomer, obtain mixing solutions;
At 10 ~ 40 DEG C, be there is ring-opening polymerization in described mixing solutions, obtain poly-rac-rac-Lactide.
Preparation process is specially: rac-rac-Lactide, under the inert atmosphere of anhydrous and oxygen-free, is dissolved in solvent by (1), under stirring, adds the solution of the title complex shown in formula I;
(2) termination reaction, use precipitation agent to be settled out polymkeric substance, then drying obtains poly-rac-rac-Lactide.
According to the present invention, in described step (1), the temperature of reaction of ring-opening polymerization is preferably 10 ~ 40 DEG C, and more preferably temperature is 20 ~ 25 DEG C, the mol ratio of the title complex shown in rac-rac-Lactide and formula I is 200 ~ 3000: 1, and advantage of the present invention is that catalyst activity is high and selectivity good.The time of polymerization is 10 ~ 120min; Described solvent is selected from: the one in toluene, benzene, methylene dichloride or tetrahydrofuran (THF).
According to the present invention, the title complex shown in formula I can directly be added in polymerization system as catalyzer, but takes more convenient after wiring solution-forming.The solvent of catalyst solution is toluene, benzene, methylene dichloride or tetrahydrofuran (THF).According to the present invention, in step (2), the percent by volume of the methanol solution of hydrochloric acid is 4 ~ 6%.If no special instructions, other chemical feedstockss all are commercial goods.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. amido bridged linkage bis aryloxy rare earth metal alkoxide complexes synthesis of the present invention is convenient, and yield is high.
2. amido bridged linkage bis aryloxy rare earth metal alkoxide complexes of the present invention is high as the activity of 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 gained polylactide is all master with assorted, and poly-butyrolactone is based on a rule.
Be below the specific embodiment of the invention, introduce the experiment effect of technical scheme of the present invention and excellence in detail.Wherein Cp is cyclopentadienyl; H
2l is amido bridged bis-phenol; Bu
tfor the tertiary butyl.
Embodiment 1
Preparation [ONNO] YCp (THF) (R
1=R
2=Bu
t)
At 25 DEG C, by 3.05 mmole H
2the tetrahydrofuran solution of L joins containing Cp
3the tetrahydrofuran solution (3.05 mmole) of Y (THF), after reaction 1h, pumps solvent, add 20 ml n-hexanes and add extraction heat, centrifugal, clear liquid shifts, hold over night at 25 DEG C, separates out clear crystal 2.06 grams (2.14 mmole), productive rate 70%.
Ultimate analysis is obtained: C, 68.59 by detecting; 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 is successfully prepared.
Embodiment 2
Preparation [ONNO] LaCp (THF) (R
1=R
2=Bu
t)
At 25 DEG C, by 2.24 mmole H
2the tetrahydrofuran solution of L joins containing Cp
3the tetrahydrofuran solution (2.24 mmole) of La (THF), after reaction 1h, pumps solvent, add 25 ml n-hexanes and add extraction heat, centrifugal, clear liquid shifts, hold over night at 25 DEG C, separates 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 is successfully prepared.
Embodiment 3
Preparation [ONNO] Y (OCH
2cF
3) (THF).
At 25 DEG C, by 6.76 mmole H
2the tetrahydrofuran solution of L joins containing Cp
3the tetrahydrofuran solution (6.76 mmole) of Y (THF), after reaction 1h, then joins in above-mentioned reaction solution by the tetrahydrofuran solution of 6.76 mmole trifluoroethanols, and 60 DEG C are continued stirring reaction 12h.
Pump solvent, add 20 milliliters of toluene and add extraction heat, centrifugal, clear liquid shifts, hold over night at 25 DEG C, separates 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 is successfully prepared.
Embodiment 4
Preparation [ONNO] Yb (OCH
2cF
3) (THF).
At 25 DEG C, by 4.86 mmole H
2the tetrahydrofuran solution of L joins containing Cp
3the tetrahydrofuran solution (4.86 mmole) of Yb (THF), after reaction 1h, then joins in above-mentioned reaction solution by the tetrahydrofuran solution of 4.86 mmole trifluoroethanols, and 60 DEG C are continued stirring reaction 12h.
Pump solvent, add 20 milliliters of toluene and add extraction heat, centrifugal, clear liquid shifts, hold over night at 25 DEG C, separates 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 is successfully prepared.
Embodiment 5
Preparation [ONNO] Er (OCH
2cF
3) (THF).
At 25 DEG C, by 2.29 mmole H
2the tetrahydrofuran solution of L joins containing Cp
3the tetrahydrofuran solution (2.29 mmole) of Er (THF), after reaction 1h, then joins in above-mentioned reaction solution by the tetrahydrofuran solution of 2.29 mmole trifluoroethanols, and 60 DEG C are continued stirring reaction 12h.
Pump solvent, add 15 milliliters of toluene and add extraction heat, centrifugal, clear liquid shifts, hold over night at 25 DEG C, separates 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 is successfully prepared.
Embodiment 6
[ONNO] Y (OCH
2cF
3) ring-opening polymerization of (THF) catalysis rac-beta-butyrolactone.
In the reaction flask through dehydration and deoxidation process, under argon shield, add rac-beta-butyrolactone 0.38 gram (4.42 mmole), add 0.71 milliliter of toluene, after stirring 5min at 25 DEG C, add catalyzer 1.15 milliliter (9.6 × 10
-3mmole), 25 DEG C of polymerization 10min, by the alcohol termination reaction containing 5% hydrochloric acid;
The industrial alcohol precipitation of polymkeric substance, must gather butyrolactone 0.36 gram, productive rate 95% to constant weight after vacuum-drying.The theoretical molecular of polymkeric substance is 3.27 ten thousand [M
n(calcd)=86 × 400 × 95%], GPC surveys number-average molecular weight (M
n) be 4.91 ten thousand, molecular weight distribution (M
w/ M
n) be 1.29, a rule content is 83%.
Embodiment 7
[ONNO] Y (OCH
2cF
3) ring-opening polymerization of (THF) catalysis rac-beta-butyrolactone
In the reaction flask through dehydration and deoxidation process, under argon shield, add rac-beta-butyrolactone 0.49 gram (5.70 mmole), add 2.26 milliliters of toluene, after stirring 5min at 25 DEG C, add catalyzer 0.59 milliliter (9.6 × 10
-3mmole), 25 DEG C of polymerization 10min, by the alcohol termination reaction containing 5% hydrochloric acid;
The industrial alcohol precipitation of polymkeric substance, must gather butyrolactone 0.36 gram, productive rate 80% to constant weight after vacuum-drying.The theoretical molecular of polymkeric substance is 6.88 ten thousand [M
n(calcd)=86 × 1000 × 80%], GPC surveys number-average molecular weight (M
n) be 8.64 ten thousand, molecular weight distribution (M
w/ M
n) be 1.37, a rule content is 82%.
Embodiment 8
[ONNO] Yb (OCH
2cF
3) ring-opening polymerization of (THF) catalysis rac-beta-butyrolactone
In the reaction flask through dehydration and deoxidation process, under argon shield, add rac-beta-butyrolactone 0.58 gram (6.74 mmole), add 2.26 milliliters of toluene, after stirring 5min at 25 DEG C, add catalyzer 2.16 milliliter (9.3 × 10
-3mmole), 25 DEG C of polymerization 10min, by the alcohol termination reaction containing 5% hydrochloric acid;
The industrial alcohol precipitation of polymkeric substance, must gather butyrolactone 0.55 gram, productive rate 94% to constant weight after vacuum-drying.The theoretical molecular of polymkeric substance is 4.85 ten thousand [M
n(calcd)=86 × 600 × 94%], GPC surveys number-average molecular weight (M
n) be 6.08 ten thousand, molecular weight distribution (M
w/ M
n) be 1.19, a rule content is 84%.
Embodiment 9
[ONNO] Yb (OCH
2cF
3) ring-opening polymerization of (THF) catalysis rac-beta-butyrolactone
In the reaction flask through dehydration and deoxidation process, under argon shield, add rac-beta-butyrolactone 0.38 gram (4.42 mmole), add 1.02 milliliters of toluene, after stirring 5min at 25 DEG C, add catalyzer 1.19 milliliter (9.3 × 10
-3mmole milliliter
-1), 25 DEG C of polymerization 10min, by the alcohol termination reaction containing 5% hydrochloric acid;
The industrial alcohol precipitation of polymkeric substance, must gather butyrolactone 0.37 gram, productive rate 97% to constant weight after vacuum-drying.The theoretical molecular of polymkeric substance is 3.34 ten thousand [M
n(calcd)=86 × 400 × 97%], GPC surveys number-average molecular weight (M
n) be 3.58 ten thousand, molecular weight distribution (M
w/ M
n) be 1.22, a rule content is 83%.
Embodiment 10
[ONNO] Er (OCH
2cF
3) ring-opening polymerization of (THF) catalysis rac-beta-butyrolactone
In the reaction flask through dehydration and deoxidation process, under argon shield, add rac-beta-butyrolactone 0.37 gram (4.30 mmole), add 0.93 milliliter of toluene, after stirring 5min at 25 DEG C, add catalyzer 1.22 milliliter (8.8 × 10
-3mmole milliliter
-1), 25 DEG C of polymerization 5min, by the alcohol termination reaction containing 5% hydrochloric acid;
The industrial alcohol precipitation of polymkeric substance, must gather butyrolactone 0.35 gram, productive rate 94% to constant weight after vacuum-drying.The theoretical molecular of polymkeric substance is 3.23 ten thousand [M
n(calcd)=86 × 400 × 94%], GPC surveys number-average molecular weight (M
n) be 3.64 ten thousand, molecular weight distribution (M
w/ M
n) be 1.31, a rule content is 83%.
Embodiment 11
The ring-opening polymerization of [ONNO] Er (OCH2CF3) (THF) catalysis rac-beta-butyrolactone
In the reaction flask through dehydration and deoxidation process, under argon shield, add rac-beta-butyrolactone 0.55 gram (6.40 mmole), add 2.00 milliliters of toluene, after stirring 5min at 25 DEG C, add catalyzer 1.20 milliliter (8.8 × 10
-3mmole milliliter
-1), 25 DEG C of polymerization 10min, by the alcohol termination reaction containing 5% hydrochloric acid;
The industrial alcohol precipitation of polymkeric substance, must gather butyrolactone 0.52 gram, productive rate 94% to constant weight after vacuum-drying.The theoretical molecular of polymkeric substance is 4.85 ten thousand [M
n(calcd)=86 × 600 × 94%], GPC surveys number-average molecular weight (M
n) be 4.68 ten thousand, molecular weight distribution (M
w/ M
n) be 1.26, a rule content is 82%.
Embodiment 12
[ONNO] Y (OCH
2cF
3) ring-opening polymerization of (THF) catalysis rac-rac-Lactide
In the reaction flask through dehydration and deoxidation process, under argon shield, add rac-rac-Lactide 0.32 gram (2.22 mmole), add 1.59 milliliters of tetrahydrofuran (THF)s, after stirring 5min at 25 DEG C, add catalyzer 0.62 milliliter (8.9 × 10
-3mmole), 25 DEG C of polymerization 1h, by the alcohol termination reaction containing 5% hydrochloric acid;
The industrial alcohol precipitation of polymkeric substance, obtains polylactide 0.31 gram, productive rate 98% to constant weight after vacuum-drying.
Adopt routine techniques to survey the molecular weight of polymkeric substance, specifically comprise the following steps: tetrahydrofuran solution polymkeric substance being made into desired concn, determining molecular weight and molecular weight distribution on the PL-50 type gel permeation chromatograph that PL company produces.Test condition: temperature 40 DEG C, tetrahydrofuran (THF) makes eluent, leacheate flow velocity 1.0 milliliters/min.The theoretical molecular of polymkeric substance is 5.64 ten thousand [M
n(calcd)=144 × 400 × 98%], GPC surveys number-average molecular weight (M
n) be 5.78 ten thousand, molecular weight distribution (M
w/ M
n) be 1.06, assorted is 99% with content.
Embodiment 13
[ONNO] Yb (OCH
2cF
3) ring-opening polymerization of (THF) catalysis rac-rac-Lactide
In the reaction flask through dehydration and deoxidation process, under argon shield, add rac-rac-Lactide 0.60 gram (4.18 mmole), add 1.59 milliliters of tetrahydrofuran (THF)s, after stirring 5min at 25 DEG C, add catalyzer 0.32 milliliter (8.6 × 10
-3mmole), 25 DEG C of polymerization 1h, by the alcohol termination reaction containing 5% hydrochloric acid;
The industrial alcohol precipitation of polymkeric substance, obtains polylactide 0.50 gram, productive rate 84% to constant weight after vacuum-drying.
Adopt routine techniques to survey the molecular weight of polymkeric substance, specifically comprise the following steps: tetrahydrofuran solution polymkeric substance being made into desired concn, determining molecular weight and molecular weight distribution on the PL-50 type gel permeation chromatograph that PL company produces.Test condition: temperature 40 DEG C, tetrahydrofuran (THF) makes eluent, leacheate flow velocity 1.0 milliliters/min.The theoretical molecular of polymkeric substance is 18.14 ten thousand [M
n(calcd)=144 × 1500 × 84%], GPC surveys number-average molecular weight (M
n) be 16.96 ten thousand, molecular weight distribution (M
w/ M
n) be 1.05, assorted is 99% with content.
By above embodiment, can prove, 1. amido bridged linkage bis aryloxy rare earth metal trifluoro ethoxy title complex synthesis of the present invention is convenient, and yield is high.2. amido bridged linkage bis aryloxy rare earth metal trifluoro ethoxy title complex of the present invention is high as the activity of 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 gained polylactide is all master with assorted, and poly-butyrolactone is based on a rule.
Above a kind of amido bridged linkage bis aryloxy rare earth metal trifluoro ethoxy title complex provided by the invention and Synthesis and applications thereof are described in detail, apply specific case herein to set forth principle of the present invention and embodiment, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping, should be understood that, for those skilled in the art, under the premise without departing from the principles of the invention, some improvement and modification can also be carried out to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (8)
1. the title complex shown in formula I,
Wherein, Ln is lanthanum, erbium or ytterbium; R
1and R
2be respectively hydrogen, methyl or the tertiary butyl.
2. a preparation method for title complex according to claim 1, is characterized in that, comprising:
A) title complex shown in formula II is provided;
B) be there is substitution reaction in a solvent in the title complex shown in formula II and trifluoroethanol, obtain the compound shown in formula I;
Wherein, Ln is lanthanum, erbium or ytterbium; R
1and R
2be respectively hydrogen, methyl or the tertiary butyl.
3. preparation method according to claim 2, is characterized in that, step a) is specially:
A1) by the amido bridging bis-phenol shown in formula III and tricyclopentadienyl rare earth compounding (C
5h
5)
3ln (THF) is mixed with the title complex shown in formula II;
Wherein, R
1and R
2be respectively hydrogen, methyl or the tertiary butyl.
4. preparation method according to claim 2, is characterized in that, step b) be specially:
B1) under anhydrous and oxygen-free, the title complex shown in formula II is mixed in a solvent for 1:1 ~ 1.05 with trifluoroethanol in molar ratio, substitution reaction 10 ~ 20h occurs, removes described solvent, obtain crude product;
B2) extract described crude product with toluene, removing precipitation, concentrated extract, obtains crystal at 0 ~ 5 DEG C, the compound namely shown in formula I.
5. the preparation method according to claim 2 or 4, is characterized in that, described solvent is aromatic solvents or ether solvent.
6. preparation method according to claim 2, is characterized in that, step b) described in the temperature of substitution reaction be 10 ~ 90 DEG C.
7. a preparation method for poly-rac-beta-butyrolactone, is characterized in that, comprising:
Be 1: 200 ~ 3000 mix in a solvent in molar ratio by title complex according to claim 1 and rac-beta-butyrolactone monomer, obtain mixing solutions;
At 10 ~ 70 DEG C, be there is ring-opening polymerization in described mixing solutions, obtain poly-rac-beta-butyrolactone.
8. a preparation method for poly-rac-rac-Lactide, is characterized in that, comprising:
Be 1: 200 ~ 3000 mix in a solvent in molar ratio by title complex according to claim 1 and rac-lactide monomer, obtain mixing solutions;
At 10 ~ 40 DEG C, be there is ring-opening polymerization in described mixing solutions, obtain poly-rac-rac-Lactide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210170636.1A CN102702241B (en) | 2012-05-29 | 2012-05-29 | Amino-bridged bis(aryloxide) rare earth metal alkoxy complexes as well as preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210170636.1A CN102702241B (en) | 2012-05-29 | 2012-05-29 | Amino-bridged bis(aryloxide) rare earth metal alkoxy complexes as well as preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102702241A CN102702241A (en) | 2012-10-03 |
| CN102702241B true CN102702241B (en) | 2015-07-15 |
Family
ID=46895338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210170636.1A Expired - Fee Related CN102702241B (en) | 2012-05-29 | 2012-05-29 | Amino-bridged bis(aryloxide) rare earth metal alkoxy complexes as well as preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102702241B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107573490B (en) * | 2017-09-07 | 2019-06-28 | 苏州大学 | The method for preparing L- lactide and 6-caprolactone random copolymer |
| CN112062944B (en) * | 2020-09-21 | 2022-05-10 | 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 |
| CN115612081B (en) * | 2022-10-25 | 2023-05-12 | 苏州大学 | Preparation method of cyclic poly (L-lactide) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1911935A (en) * | 2006-08-25 | 2007-02-14 | 中国科学院长春应用化学研究所 | Catalytic lactide stereo selectirity poly rare earth compound |
-
2012
- 2012-05-29 CN CN201210170636.1A patent/CN102702241B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1911935A (en) * | 2006-08-25 | 2007-02-14 | 中国科学院长春应用化学研究所 | Catalytic lactide stereo selectirity poly rare earth compound |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis, Characterization, and Reactivity of Amine Bis(phenolato) Cyclopentadienyl Lanthanide Complexes;Zhou, Lanzhi et al.;《Journal of Rare Earths》;20070531;第25卷(第5期);第544-548页 * |
| Well-defined bis(phenolate) lanthanide methoxides as efficient initiators for the polymerization of cyclic carbonate and lactide;Xu, XiaoPing et al.;《Chinese Science Bulletin》;20070630;第52卷(第12期);第1623-1628页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102702241A (en) | 2012-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ren et al. | Stereoregular polycarbonate synthesis: alternating copolymerization of CO2 with aliphatic terminal epoxides catalyzed by multichiral cobalt (III) complexes | |
| Li et al. | Asymmetric, regio‐and stereo‐selective alternating copolymerization of CO2 and propylene oxide catalyzed by chiral chromium Salan complexes | |
| CN102702241B (en) | Amino-bridged bis(aryloxide) rare earth metal alkoxy complexes as well as preparation and application thereof | |
| Liu et al. | Alternating copolymerization of carbon dioxide and propylene oxide under bifunctional cobalt salen complexes: Role of Lewis base substituent covalent bonded on salen ligand | |
| CN105111426B (en) | Quaternary ammonium salt functionalized porphyrin catalyst and preparation method thereof | |
| CN109354593B (en) | N, N-bidentate chiral rare earth metal complex, preparation method and application | |
| US9249120B2 (en) | Conjugated microporous macromolecule catalyst complexed with cobalt, preparation and use thereof | |
| WO2024087581A1 (en) | Preparation method for cyclic poly(l-lactide) | |
| CN101412727B (en) | Imidazolidinyl bridged bis(aryloxide) rare-earth metal aminate and catalysis use thereof | |
| Ho et al. | Copolymerization of carbon dioxide with cyclohexene oxide catalyzed by bimetallic dysprosium complexes containing hydrazine‐functionalized Schiff‐base derivatives | |
| CN102050842B (en) | Bimetallic complex and application thereof | |
| CN103242353A (en) | Pincer-like rare earth complex, and synthesis method and application thereof | |
| CN103566970A (en) | Chromium, zinc or copper complexed conjugated microporous polymer catalysts, as well as preparation method and application thereof | |
| CN103254246B (en) | A kind of Rare earth-zinc bimetallic carboxylic group compound and preparation method thereof and application | |
| Ni et al. | Controlled ring‐opening polymerization of ε‐caprolactone initiated by in situ formed yttrium trisalicylaldimine complexes, and their study by density functional theory | |
| CN100406492C (en) | Ring-opening polymerization catalyst for lactide and process for preparing same | |
| CN113896875B (en) | Intramolecular trifunctional Lewis acid-base pair catalyst, annular topological structure PMMBL polymer, preparation method and application | |
| CN103936974B (en) | A kind of rare earth metal complex catalyzer and method for making thereof and application | |
| CN101845111B (en) | Method for preparing conjugated diene polymer | |
| CN101602784B (en) | Amino aryloxy rare earth metal amide and application thereof | |
| CN101418006A (en) | N-aryloxy functionalized ketimine rare earth metal amido and catalytic use thereof | |
| CN102558246B (en) | Bimetal benzyloxy compound and preparation method and application thereof | |
| CN105482092A (en) | Synthesizing method of carbon dioxide-based polymer | |
| CN107286280A (en) | The coordination polymerization preparation method of Isosorbide-5-Nitrae-poly- 3- methylene cyclopentenes | |
| CN106188363B (en) | Cis- 1,4- polymer of 2- aryl -1,3- butadiene and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150715 Termination date: 20180529 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |