CN115260217B - Bridged bisoxazoline rare earth metal catalyst, preparation method and application - Google Patents

Bridged bisoxazoline rare earth metal catalyst, preparation method and application Download PDF

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CN115260217B
CN115260217B CN202210996297.6A CN202210996297A CN115260217B CN 115260217 B CN115260217 B CN 115260217B CN 202210996297 A CN202210996297 A CN 202210996297A CN 115260217 B CN115260217 B CN 115260217B
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earth metal
bisoxazoline
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CN115260217A (en
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焉晓明
侯鑫
潘昱
贺高红
郝名洋
孙兴润
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Dalian University of Technology
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Abstract

The invention belongs to the technical field of catalysis, and relates to a bridged bisoxazoline rare earth metal catalyst, a preparation method and application thereof. The rare earth metal catalyst prepared by the invention takes amino alcohol which is cheap and easy to obtain and easy to modify as a raw material, and the synthesized ligands with different bridging structures and different substituents can directly react with rare earth metal alkylate, so that the catalyst is easy to separate and purify and has high yield. The catalyst can be directly used for catalyzing ring-opening polymerization of cyclic lactone at room temperature, and has higher catalytic activity.

Description

Bridged bisoxazoline rare earth metal catalyst, preparation method and application
Technical Field
The invention belongs to the technical field of catalysis, and relates to a bridged bisoxazoline rare earth metal catalyst, a preparation method and application thereof.
Background
The polyester material is a typical representative of degradable high polymer material, is a biological-based high polymer applied to production and living, is different from the problems of high exploitation cost, difficult degradation of polymers and the like faced by some petroleum-based plastic products, has abundant sources, low price, good biocompatibility and capability of realizing biodegradation, and is widely applied to the fields of food packaging, medical equipment and the like. In recent years, research on ring-opening polymerization of cyclic lactones catalyzed by rare earth metal catalysts is attracting more and more attention from researchers. The Cui subject group reports rare earth metal catalysts with dialkyl initiating groups, which can catalyze ring-opening polymerization of epsilon-CL with high activity, and the synthesized polymer has narrower molecular weight distribution (pdi=1.17). (organometallics, 2008,27,5889-5893). The Zhou subject group reports that bisphenol tetradentate rare earth catalyst bridged by carbon atoms catalyzes epsilon-CL to realize high activity at room temperature, and the catalytic system is a controllable system and accords with coordination-insertion mechanism. (RSC advance, 2016,6,22269-22276). In addition, polymer materials with different physical properties can be prepared by regulating the microstructure of the polymer. Therefore, it is of great importance to design a class of high performance catalysts that catalyze the polymerization of cyclic lactones.
Disclosure of Invention
The invention aims to provide a preparation method of a bridged bisoxazoline rare earth metal catalyst and application thereof in the field of ring-opening polymerization of cyclic lactone, wherein the rare earth metal catalyst has an adjustable bridged framework.
The technical scheme of the invention is as follows:
a bridged bisoxazoline rare earth metal catalyst has the following structural formula:
Wherein Ln is a rare earth metal, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, or lutetium;
R 1 is a substituent on the carbon linked to nitrogen on the oxazoline heterocycle, which is a hydrogen atom or methyl;
r 2 is a substituent on the carbon attached to the nitrogen on the oxazoline heterocycle, which is a hydrogen atom, methyl, isopropyl, tert-butyl, phenyl, benzyl or adamantyl;
R 3 is a group directly connected with rare earth metal, and is a methyl, ethyl, isopropyl, n-butyl, tert-butyl, phenyl, benzyl, trimethylsilyl, alkoxy, indenyl, fluorenyl or halogen atom; wherein, halogen atoms are Cl, br and I;
l is an auxiliary ligand directly connected with rare earth metal, and is tetrahydrofuran, anisole, dimethyl ether, diethyl ether, tetrahydropyran or triethylamine; wherein m=0 to 2;
n is the number of bridging methylene groups, n=2 to 6.
The preparation method of the bridged bisoxazoline rare earth metal catalyst comprises the following steps:
(1) Preparation of bridged bisoxazoline ligands
Under the condition of nitrogen, dissolving an o-bromobenzene-oxazoline, a diamino compound, tris (dibenzylideneacetone) dipalladium, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine and sodium tert-butoxide in a toluene solution with the concentration of 0.1-1.0M, heating and refluxing for 12 hours, and separating to obtain a bridged bisoxazoline ligand; wherein, the mol ratio of the o-bromobenzene-oxazoline, the diamino compound, the tris (dibenzylideneacetone) dipalladium, the 1,1 '-binaphthyl-2, 2' -bisdiphenylphosphine and the sodium tert-butoxide is 2:1:0.02:0.04:3; the diamino compound is ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylene diamine, 1, 6-hexamethylenediamine or 1,1 '-binaphthyl-2, 2' -diamine;
(2) Preparation of bridged bisoxazoline rare earth metal catalysts
Under the condition of nitrogen protection and low temperature, dissolving bridging ligand in toluene solution with the concentration of 0.01-0.1M, dissolving alkyl metal in n-hexane solution with the concentration of 0.01-0.1M, and then mixing the two solutions to react for 1-3 hours to obtain the bridging bisoxazoline rare earth metal catalyst, wherein the molar ratio of the bridging bisoxazoline ligand to the alkyl rare earth metal is 1:1-1.2; the volume ratio of toluene to n-hexane is 1:2-6.
A bridged bisoxazoline rare earth metal catalyst is applied to ring-opening polymerization reaction of cyclic lactone, and the steps of the catalytic polymerization reaction are as follows:
Stirring the rare earth metal catalyst and the cyclic lactone in a good solvent for 30s-12h under the protection of nitrogen, adding a chain terminator to terminate the reaction after a certain time, separating out reaction liquid in a separating-out liquid, settling to obtain a solid polymer, and then vacuum drying the obtained polymer to constant weight at 30-70 ℃; the concentration of the rare earth metal catalyst in the reaction system is 1 multiplied by 10 -3～5×10-2 mol/L, and the molar ratio of the cyclic lactone to the rare earth metal catalyst is 50-5000:1.
The cyclic lactone types are L-lactide, D-lactide, rac-lactide, meso-lactide, beta-butyrolactone, epsilon-caprolactone and gamma-valerolactone; when the cyclic lactone is L-lactide, D-lactide, rac-lactide, meso-lactide, epsilon-caprolactone or gamma-valerolactone, the polymerization time is 5-30min; when the cyclic lactone is beta-butyrolactone, the polymerization time is 1-3h.
The good solvent is one or more of benzene, toluene, chlorobenzene, dichloromethane or tetrahydrofuran.
The chain terminator is methanol, ethanol, propanol, n-butanol, isobutanol, tertiary butanol or the solution containing HCl, wherein the volume ratio of the HCl to the solution is 5% -10%: 1.
The filtrate is methanol, ethanol, propanol, n-butanol, isobutanol, tertiary butanol or the solution containing HCl, wherein the volume ratio of the HCl to the solution is 5% -10%: 1.
The invention has the beneficial effects that: (1) The bridged bisoxazoline ligand is simple and easy to synthesize and operate and easy to modify; (2) The bridged bisoxazoline rare earth metal catalyst has simple preparation method, the ligand can directly react with alkyl rare earth metal, and the catalyst is easy to separate and purify; (3) The bridged bisoxazoline rare earth metal catalyst can be directly applied to ring-opening polymerization of cyclic lactones.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of ligand (MePh) 2-(CH2)4.
FIG. 2 is a nuclear magnetic hydrogen spectrum of catalyst (MePh) 2-(CH2)4-Y(CH2SiMe3).
FIG. 3 is a nuclear magnetic hydrogen spectrum of ligand (MePh) 2-Ph4.
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of catalyst (MePh) 2-Ph4-Y(CH2SiMe3) (THF).
FIG. 5 is a GPC chart of polycaprolactone.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described below with reference to examples.
Example 1
Preparation of catalyst (MePh) 2-(CH2)4-Y(CH2SiMe3)
(1) Preparation of ligand (MePh) 2-(CH2)4
O-bromobenzene-oxazoline (1 g,3.94 mmol), 1, 4-butanediamine (0.1736 g,1.97 mmol), tris (dibenzylideneacetone) dipalladium (0.07 g,0.0787 mmol), 1 '-binaphthyl-2, 2' -bisdiphenylphosphine (0.098 g,0.1576 mmol) and sodium tert-butoxide (0.618 g,5.91 mmol) were added in sequence to a Schlenk flask under nitrogen, dissolved in 25ml toluene and heated at 95℃under reflux for 24h, after the reaction was completed, the solvent was removed by filtration and column chromatography gave 1.21g of ligand in 71.0% yield. The nuclear magnetic hydrogen spectrum of the ligand is shown in figure 1. (2) Preparation of catalyst (MePh) 2-(CH2)4-Y(CH2SiMe3)
Ligand (MePh) 2-(CH2)4 (0.1 g,0.2304 mmol) was dissolved in 1ml toluene and yttrium alkyl (0.1138 g,0.2304 mmol) was dissolved in 3ml n-hexane under nitrogen, stirred and mixed at-30 ℃, slowly warmed to room temperature for 2h, filtered, and the solvent was removed under vacuum to give catalyst 0.956g in 68.2% yield. The nuclear magnetic hydrogen spectrum of the catalyst is shown in figure 2.
Example 2
Preparation of catalyst (MePh) 2-(CH2)4-Lu(CH2SiMe3)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to the method of example 1, except that Lu (CH 2SiMe3)3(THF)2 instead of Y (CH 2SiMe3)3(THF)2) was used, giving 0.11g of catalyst, 69.8% yield.
Example 3
Preparation of catalyst (MePh) 2-(CH2)4-Sc(CH2SiMe3)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to the method in example 1, except that Sc (CH 2SiMe3)3(THF)2 was used instead of Y (CH 2SiMe3)3(THF)2, giving a catalyst of 0.12g, 71.8% yield).
Example 4
Preparation of catalyst (iPrPh)2-(CH2)4-Y(CH2SiMe3)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to the method in example 1, except that ligand (iPrPh)2-(CH2)4 was used instead of ligand (MePh) 2-(CH2)4, giving 0.09g of catalyst in 58.4% yield.
Example 5
Preparation of catalyst (PhPh) 2-(CH2)4-Y(CH2SiMe3)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to the method in example 1, except that ligand (PhPh) 2-(CH2)4 was used instead of ligand (MePh) 2-(CH2)4, giving catalyst 0.078g, 58.1% yield.
Example 6
Preparation of catalyst (MePh) 2-(CH2)2-Y(CH2SiMe3)
(1) Synthesis of ligand (MePh) 2-(CH2)2
The ligand was prepared in the same manner as in example 1, as follows:
the procedure was analogous to the method of example 1, except that ethylenediamine was used instead of 1, 4-butanediamine, 1.53g of ligand was obtained, in 70% yield.
(2) Synthesis of catalyst (MePh) 2-(CH2)2-Y(CH2SiMe3)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to the method of example 1, giving 0.12g of catalyst in 85.6% yield.
Example 7
Preparation of catalyst (MePh) 2-(CH2)2-Lu(CH2SiMe3)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to that in example 1, except that Lu (CH 2SiMe3)3(THF)2 was used instead of Y (CH 2SiMe3)3(THF)2, giving 0.11g of catalyst, 65.0% yield).
Example 8
Preparation of catalyst (MePh) 2-(CH2)2-Sc(CH2SiMe3)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to the method in example 1, except that Sc (CH 2SiMe3)3(THF)2 was used instead of Y (CH 2SiMe3)3(THF)2, giving 0.10g of catalyst, 62.3% yield).
Example 9
Preparation of catalyst (MePh) 2-Ph4-Y(CH2SiMe3) (THF)
(1) Synthesis of ligand (MePh) 2-Ph4
The ligand was prepared in the same manner as in example 1, as follows:
The procedure was analogous to the method of example 1, except that 1,1 '-binaphthyl-2, 2' -diamine was used instead of 1, 4-butanediamine, 1.53g of ligand was obtained, yield 70%. The nuclear magnetic hydrogen spectrum of the ligand is shown in figure 3.
(2) Synthesis of catalyst (MePh) 2-Ph4-Y(CH2SiMe3) (THF)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to the method of example 1, giving 0.12g of catalyst in 85.6% yield. The nuclear magnetic hydrogen spectrum of the catalyst is shown in fig. 4.
Example 10
Preparation of catalyst (MePh) 2-Ph4-Lu(CH2SiMe3) (THF)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to the method in example 1, except that Lu (CH 2SiMe3)3(THF)2 was used instead of Y (CH 2SiMe3)3(THF)2, giving 0.09g of catalyst, 55.0% yield).
Example 11
Preparation of catalyst (MePh) 2-Ph4-Sc(CH2SiMe3) (THF)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to the method of example 1, except that Sc (CH 2SiMe3)3(THF)2 was used instead of Y (CH 2SiMe3)3(THF)2, giving 0.08g of catalyst, 45.4% yield).
Example 12
Preparation of catalyst (MePh) 2-(CH2)4 -Y (Cl) (THF)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to the method of example 1, except that YCl 3(THF)2 was used instead of Y (CH 2SiMe3)3(THF)2, giving 0.09g of catalyst, 50.8% yield.
Example 13
Preparation of catalyst (iPrPh)2-(CH2)4 -Y (Cl) (THF)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure is analogous to the method in example 1, except that ligand (iPrPh)2-(CH2)4 is used instead of ligand (MePh) 2-(CH2)4 and YCl 3(THF)2 is used instead of Y (CH 2SiMe3)3(THF)2) to give product 0.08g in 47.1% yield.
Example 14
Preparation of catalyst (PhPh) 2-(CH2)4 -Y (Cl) (THF)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure is analogous to the method in example 1, except that ligand (PhPh) 2-(CH2)4 is used instead of ligand (MePh) 2-(CH2)4 and YCl 3(THF)2 is used instead of Y (CH 2SiMe3)3(THF)2, giving product 0.09g, 52.2% yield.
Example 15
Implementation of the polymerization reaction
In a glove box, (MePh) 2-(CH2)4-Y(CH2SiMe3) (10 μmol,6.09 mg) of catalyst and ε -caprolactone (2 mmol,228.3 mg) were added sequentially to a 20mL reaction flask, 2mL toluene solvent was added, and the reaction was stirred at room temperature for 5min; the polymerization termination process is as follows: adding a chain terminator to terminate the reaction; the reaction solution is separated out by absolute ethyl alcohol, solid polymer is obtained by sedimentation, and finally, the polymer is dried to constant weight in vacuum at 45 ℃ to obtain 206.0mg of polycaprolactone, the conversion rate is 99%, and the catalytic activity is 2376.h -1. The polycaprolactone GPC chart is shown in FIG. 5.
Example 16
The procedure is as in example 15, except that the catalyst is replaced by (MePh) 2-(CH2)4-Lu(CH2SiMe3) (MePh) 2-(CH2)4-Y(CH2SiMe3 to give 212.3mg of polycaprolactone with a conversion of 99% and a catalytic activity of 2376.h -1.
Example 17
The procedure is as in example 15, except that the catalyst is replaced by (MePh) 2-(CH2)4-Sc(CH2SiMe3) (MePh) 2-(CH2)4-Y(CH2SiMe3 to give 209.5mg of polycaprolactone with a conversion of 90% and a catalytic activity of 2160.h -1.
Example 18
The procedure is as in example 15, except that the catalyst is replaced by (MePh) 2-Ph4-Y(CH2SiMe3) (THF) (MePh) 2-(CH2)4-Y(CH2SiMe3 to give 210.5mg of polycaprolactone with a conversion of 99% and a catalytic activity of 1188.h -1.
Example 19
In a glove box, (MePh) 2-(CH2)4-Y(CH2SiMe3) (10 μmol,6.09 mg) of catalyst and rac-lactide (2 mmol,288.3 mg) were sequentially added to a 20mL reaction flask, 2mL THF solvent was added and the reaction stirred at room temperature for 10min; the polymerization termination process is as follows: adding a chain terminator to terminate the reaction; and (3) separating out the reaction solution by using absolute ethyl alcohol, settling to obtain a solid polymer, and finally, vacuum drying the polymer at 45 ℃ to constant weight to obtain 256.4mg of polylactide, wherein the conversion rate is 99%, and the catalytic activity is 1188.h -1.
Example 20
The procedure is as in example 19, except that the catalyst is replaced with (MePh) 2-(CH2)4-Lu(CH2SiMe3) (MePh) 2-(CH2)4-Y(CH2SiMe3 to give 203.8mg of polylactide with a conversion of 99% and a catalytic activity of 1188.h -1.
Example 21
The procedure is as in example 19, except that the catalyst is replaced with (MePh) 2-(CH2)4-Sc(CH2SiMe3) (MePh) 2-(CH2)4-Y(CH2SiMe3 to give 202.1mg of polylactide with a conversion of 99% and a catalytic activity of 1188.h -1.
Example 22
The procedure is as in example 19, except that the catalyst is replaced by (MePh) 2-Ph4-Y(CH2SiMe3) (THF) (MePh) 2-(CH2)4-Y(CH2SiMe3 to give 235.5mg of polylactide with a conversion of 98% and a catalytic activity of 1176.h -1.
Example 23
In a glove box, (MePh) 2-(CH2)4-Y(CH2SiMe3) (10. Mu. Mol,6.09 mg) of the catalyst and β -butyrolactone (2 mmol,172 mg) were sequentially added to a 20mL reaction flask, 2mL of toluene solvent was added, and the reaction was stirred at room temperature for 3 hours; the polymerization termination process is as follows: adding a chain terminator to terminate the reaction; the solid polymer is separated out from the reaction liquid by absolute ethyl alcohol, the obtained polymer is washed by absolute ethyl alcohol for multiple times, finally, the polymer and 45 ℃ are dried to constant weight in vacuum, 140.8mg of polybutyrolactone is obtained through reaction, and the conversion rate is 90.2%.

Claims (9)

1. The bridged bisoxazoline rare earth metal catalyst is characterized by comprising the following structural formula: wherein Ln is rare earth metal, scandium, yttrium or lutetium;
R 1 is a substituent on the carbon linked to nitrogen on the oxazoline heterocycle, which is a hydrogen atom or methyl;
R 2 is a substituent on the carbon linked with nitrogen on the oxazoline heterocycle and is a hydrogen atom, methyl, isopropyl or phenyl;
R 3 is a group directly connected with rare earth metal and is trimethylsilyl or Cl;
l is an auxiliary ligand directly connected with rare earth metal and is tetrahydrofuran; wherein m=0 to 2;
n is the number of bridging methylene groups, and n=2 to 6.
2. The use of a bridged bisoxazoline rare earth metal catalyst according to claim 1 in ring-opening polymerization of lactones, characterized by the steps of:
Under the protection of nitrogen, stirring the bridged bisoxazoline rare earth metal catalyst and the cyclic lactone in a good solvent for 30s-12h, adding a chain terminator to terminate the reaction after a certain time, separating out the reaction solution in the separated liquid, settling to obtain a solid polymer, and then vacuum drying the obtained solid polymer to constant weight at 30-70 ℃; the concentration of the bridged bisoxazoline rare earth metal catalyst in the reaction system is 1 multiplied by 10 -3~5×10-2 mol/L, and the molar ratio of the cyclic lactone to the rare earth metal catalyst is 50-5000:1;
The cyclic lactone is L-lactide, D-lactide, rac-lactide, meso-lactide, beta-butyrolactone, ɛ -caprolactone or gamma-valerolactone.
3. The use of a bridged bisoxazoline rare earth metal catalyst according to claim 2 in ring opening polymerization of a cyclic lactone, wherein the polymerization time is 5-30min when the cyclic lactone is L-lactide, D-lactide, rac-lactide, meso-lactide, ɛ -caprolactone or γ -valerolactone; when the cyclic lactone is beta-butyrolactone, the polymerization time is 1-3h.
4. The use of a bridged bisoxazoline rare earth metal catalyst according to claim 2 or 3 in ring-opening polymerization of cyclic lactones, wherein the good solvent is one or more of benzene, toluene, chlorobenzene, dichloromethane and tetrahydrofuran.
5. The use of a bridged bisoxazoline rare earth metal catalyst according to claim 2 or 3 in a ring-opening polymerization of a cyclic lactone, wherein the chain terminator is methanol, ethanol, propanol, n-butanol, isobutanol, t-butanol or the solution containing HCl, wherein the volume ratio of HCl to the solution is 5% -10%: 1.
6. The use of a bridged bisoxazoline rare earth metal catalyst according to claim 4 in a ring-opening polymerization of a cyclic lactone, wherein the chain terminator is methanol, ethanol, propanol, n-butanol, isobutanol, t-butanol or the solution containing HCl, wherein the volume ratio of HCl to the solution is 5% -10%: 1.
7. The use of a bridged bisoxazoline rare earth metal catalyst according to claim 2,3 or 6, wherein the filtrate is methanol, ethanol, propanol, n-butanol, isobutanol, t-butanol or a solution containing HCl, wherein the volume ratio of HCl to the solution is 5% -10%: 1.
8. The use of a bridged bisoxazoline rare earth metal catalyst according to claim 4, wherein the filtrate is methanol, ethanol, propanol, n-butanol, isobutanol, tert-butanol or the solution containing HCl, wherein the volume ratio of HCl to the solution is 5% -10%: 1.
9. The use of a bridged bisoxazoline rare earth metal catalyst according to claim 5, wherein the filtrate is methanol, ethanol, propanol, n-butanol, isobutanol, tert-butanol or the solution containing HCl, wherein the volume ratio of HCl to the solution is 5% -10%: 1.
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