CN117865998A - Organometallic catalyst based on tetradentate nitroxide ligand and preparation method and application thereof - Google Patents

Organometallic catalyst based on tetradentate nitroxide ligand and preparation method and application thereof Download PDF

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Publication number
CN117865998A
CN117865998A CN202410025420.9A CN202410025420A CN117865998A CN 117865998 A CN117865998 A CN 117865998A CN 202410025420 A CN202410025420 A CN 202410025420A CN 117865998 A CN117865998 A CN 117865998A
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tert
solvent
reaction
butylsalicylidene
bis
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林雅滢
戴汝熙
何媛
徐琳
徐人威
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Sinochem Quanzhou Energy Technology Co Ltd
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Sinochem Quanzhou Energy Technology Co Ltd
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Abstract

The invention discloses an organic metal catalyst based on a tetradentate nitroxide ligand, and a preparation method and application thereof, and belongs to the field of high polymer materials. The organic metal catalyst is a metal complex obtained by reacting N, N '-bis (3, 5-di-tert-butylsalicylidene) ethylenediamine with zirconium tert-butoxide, wherein N, N, O and O in N, N' -bis (3, 5-di-tert-butylsalicylidene) ethylenediamine molecules respectively provide a binding site, and the binding sites are coordinated with zirconium metal center to form the tetradentate complex. In the invention, the preparation method of the catalyst is simple, the reaction condition is mild, and the obtained metal catalyst can be used for catalyzing ring-opening polymerization of cyclic lactone. The catalyst has lower toxicity and higher catalytic activity, and can be used for catalyzing the bulk melt polymerization of cyclic lactone and the ring-opening polymerization of the cyclic lactone in a solvent.

Description

Organometallic catalyst based on tetradentate nitroxide ligand and preparation method and application thereof
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to an organic metal catalyst based on tetradentate nitrogen-oxygen ligand, and a preparation method and application thereof.
Background
Most of traditional high polymer materials are difficult to degrade in the environment, and the problems of white pollution and the like are easily caused. Therefore, development of novel materials that are environmentally friendly and biodegradable is one of the trends in the development of polymer materials. Among them, polyester materials represented by polylactic acid and polycaprolactone are attracting attention due to their characteristics of biodegradability, non-toxicity, non-irritation and good biocompatibility, and are widely used in the medical field.
Polyesters can be prepared by polycondensation of the corresponding monomeric acids or ring-opening polymerization of the corresponding cyclic lactones. The most common and efficient method is to catalyze the ring-opening polymerization of cyclic lactones using metal catalysts to produce the corresponding polyesters. Stannous octoate is the most successful metal catalyst currently used in ring opening polymerization of cyclic lactones. However, stannous octoate has slightly insufficient catalytic activity for ring opening polymerization reaction, the required reaction temperature is higher, the reaction time is longer, the monomer conversion rate is lower, and the tin element in the stannous octoate is used as a heavy metal element, has certain biotoxicity and needs to strictly control the feeding amount of the stannous octoate. Therefore, it is desirable to be able to develop other kinds of metal catalysts to replace stannous octoate. Aluminum compounds, zinc compounds, iron compounds, titanium compounds, zirconium compounds are several types of ring-opening polymerization catalysts under extensive research.
Disclosure of Invention
Based on the background, the invention provides a zirconium metal catalyst based on a tetradentate nitrogen-oxygen ligand, and a preparation method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an organometallic catalyst based on a tetradentate nitroxide ligand is a zirconium complex having the structure of N, N' -bis (3, 5-di-tert-butylsalicylidene) ethylenediamine. Wherein, N, N, O, O on N, N' -bis (3, 5-di-tert-butylsalicylidene) ethylenediamine can respectively provide coordination sites to form tetradentate metal complexes with zirconium compounds, and the chemical structural formula is as follows:
the preparation method of the metal catalyst comprises the following steps:
1) Under anhydrous and anaerobic conditions, respectively dissolving a ligand N, N '-bis (3, 5-di-tert-butylsalicylidene) ethylenediamine and zirconium tert-butoxide by using a certain amount of solvent, dropwise adding a zirconium tert-butoxide solution into the N, N' -bis (3, 5-di-tert-butylsalicylidene) ethylenediamine solution under stirring, and reacting for a period of time at a certain temperature;
2) And after the reaction is finished, removing the solvent, and recrystallizing the crude product to obtain the metal catalyst.
Further, the molar ratio of N, N' -bis (3, 5-di-tert-butylsalicylidene) ethylenediamine to zirconium tert-butoxide used in step 1) is 1:1-1:2, preferably 1:1-1:1.05;
further, the chemical structural formula of the N, N' -bis (3, 5-di-tert-butylsalicylidene) ethylenediamine in the step 1) is as follows:
further, in the step 1), dropwise adding the zirconium tert-butoxide solution into N, N' -bis (3, 5-di-tert-butylsalicylidene) ethylenediamine solution at the temperature of-20-25 ℃;
further, in the step 1), the solvent can be one or more of benzene, toluene, anhydrous diethyl ether and dichloromethane, wherein the mass of the solvent is 5-40 times of the total mass of the reaction raw materials;
further, the reaction in the step 1) needs to be started after the reaction system is restored to room temperature, the reaction temperature is 25-80 ℃ and the reaction time is 2 h-24 h;
further, the recrystallization solvent in the step 2) is one or more of benzene, toluene, xylene, trimethylbenzene, petroleum ether, n-hexane and cyclohexane.
The metal catalyst can be used for catalyzing ring-opening polymerization of cyclic lactone, and comprises the following steps:
step one: weighing a certain amount of cyclic lactone monomers and the metal catalyst in an anhydrous and anaerobic glove box;
step two: in a glove box without water and oxygen, mixing a monomer and a metal catalyst, and reacting for a period of time at a certain temperature;
step three: after the reaction system was cooled to room temperature, it was transferred to the outside of the glove box. Adding a proper amount of good solvent to dissolve the reactant completely, then dripping the obtained solution into the poor solvent, precipitating the polymer, centrifuging to remove the solvent, and drying the precipitate under vacuum to obtain the cyclic lactone polymer.
Further, in the first step, the cyclic lactone monomer is any one or two of L-lactide, D, L-lactide and epsilon-caprolactone; the ratio of the monomer to the metal catalyst is 100:1-630:1;
further, the reaction temperature in the second step is 40-180 ℃ and the reaction time is 0.5-h-8 h;
further, the reaction process in the second step can be carried out under the condition of no solvent or in a solvent, wherein the solvent is one or more of benzene, toluene, xylene, trimethylbenzene, tetrahydrofuran, methylene dichloride and propylene oxide;
further, in the third step, the good solvent is any one or more of benzene, toluene, xylene, trimethylbenzene, tetrahydrofuran, methylene dichloride, dichloroethane, chloroform and hexafluoroisopropanol;
further, in the third step, the poor solvent is any one or more of methanol, ethanol, diethyl ether, petroleum ether and n-hexane.
The invention has the beneficial effects that:
(1) The invention provides a zirconium catalyst based on a tetradentate nitrogen-oxygen ligand and a preparation method thereof, and the preparation method is mild and efficient;
(2) The zirconium catalyst based on the tetradentate nitrogen-oxygen ligand provided by the invention can be used for catalyzing ring-opening polymerization of cyclic lactone, has high catalytic activity and low toxicity, and can be used for bulk melt polymerization and solution polymerization.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the zirconium-based catalyst prepared in example 1.
FIG. 2 is a gel permeation chromatogram of the epsilon caprolactone polymer prepared in application example 1.
FIG. 3 is a gel permeation chromatogram of the L-lactide polymer prepared in application example 5.
FIG. 4 is a gel permeation chromatogram of the L-lactide- ε -caprolactone copolymer prepared in application example 9.
FIG. 5 is a gel permeation chromatogram of the D, L-lactide polymer prepared in application example 10.
Detailed Description
An organometallic catalyst based on a tetradentate nitroxide ligand, the preparation method comprising the steps of:
1) Under the anhydrous and anaerobic condition, a certain amount of solvent is used for respectively dissolving the ligand N, N' -bis (3, 5-di-tert-butylsalicylidene) ethylenediamine and zirconium tert-butoxide, the molar ratio of the ligand to the zirconium tert-butoxide is 1:1-1:2, and the total mass of the used solvent is 5-40 times of the total mass of the reaction raw materials. Dropwise adding a zirconium tert-butoxide solution into an N, N' -bis (3, 5-di-tert-butylsalicylidene) ethylenediamine solution while stirring at the temperature of-20-25 ℃, and reacting at the temperature of 25-80 ℃ after the reaction system returns to room temperature for 2 h-24 h;
2) And after the reaction is finished, vacuumizing to remove the solvent, and recrystallizing the crude product to obtain the metal catalyst.
Wherein, the structural formula of the ligand N, N' -bis (3, 5-di-tert-butylsalicylidene) ethylenediamine in the step 1) is as follows:
the solvent in the step 1) is one or more of benzene, toluene, anhydrous diethyl ether and dichloromethane.
The solvent used in the recrystallization process in the step 2) is one or more of benzene, toluene, xylene, trimethylbenzene, petroleum ether, n-hexane and cyclohexane.
The chemical structural formula of the metal catalyst obtained in the step 2) is as follows:
in order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art unless otherwise indicated.
In the following examples, various processes and methods, which are not described in detail, are conventional methods well known in the art.
Example 1
492.6 mg of N, N' -bis (3, 5-di-tert-butylsalicylidene) ethylenediamine was weighed out in an anhydrous and anaerobic glove box and dissolved in 4 mL toluene. Zirconium tert-butoxide 384.0 mg was weighed and dissolved in toluene 1 mL, and zirconium tert-butoxide was added dropwise to an N, N' -bis (3, 5-di-tert-butylsalicylidene) ethylenediamine solution at room temperature with stirring. The resulting solution was allowed to react at room temperature 2 h. After the reaction is finished, the toluene is removed by vacuum pumping, 3 mL normal hexane is added to dissolve the crude product, the obtained solution is concentrated and then is placed at the temperature of minus 20 ℃ for cooling crystallization, the solvent is removed by filtration, and the obtained solid is dried to obtain the zirconium catalyst 623.6 mg based on the tetradentate nitrogen-oxygen ligand, and the yield is 85.6%.
Example 2
The specific operation of this example was the same as in example 1, except that the ligand N, N' -bis (3, 5-di-t-butylsalicylidene) ethylenediamine was reacted with zirconium t-butoxide at 50℃to give a zirconium catalyst of quality 626.0 mg in 86.0% yield.
Application example 1
In an anhydrous and anaerobic glove box, 50.4 g mg of the zirconium catalyst obtained in example 1 and 784.4 mg epsilon-caprolactone were weighed, mixed, heated to 80 ℃ and stirred for reaction 2 h. After the reaction is finished, after the reaction system is restored to room temperature, dichloromethane is added to completely dissolve the crude product. The obtained solution was dropped into absolute ethanol, and a white solid was precipitated. Centrifuging to remove the solvent, and vacuum drying the obtained solid to obtain the polycaprolactone. The molecular weight of the obtained polycaprolactone was 275.1 kg/mol, the molecular weight distribution was 2.16 and the monomer conversion was 99.5%.
Application example 2
The specific operation of this application example was the same as that of application example 1, except that the charged amount of epsilon-caprolactone in the reaction was 1.0102 and g, and the charged amount of zirconium catalyst was 10.2 mg. The polycaprolactone obtained by the reaction has a molecular weight of 466.5 kg/mol, a molecular weight distribution of 2.01 and a monomer conversion of 99.4%.
Application example 3
The specific operation of this application example was the same as that of application example 1, except that the charged amount of epsilon-caprolactone in the reaction was 789.0 mg, the charged amount of zirconium catalyst was 8.4 mg, and 2 mL toluene was added to the reaction system. The molecular weight of the polycaprolactone obtained by the reaction is 389.7 kg/mol, the molecular weight distribution is 2.01, and the monomer conversion rate is 99.2%.
Application example 4
The specific operation of this application example was the same as that of application example 1, except that the charged amount of epsilon-caprolactone in the reaction was 751.6 mg, the charged amount of zirconium catalyst was 8.3 mg, and the reaction time was 0.5 h. The molecular weight of the polycaprolactone obtained by the reaction is 337.7 kg/mol, the molecular weight distribution is 2.20, and the monomer conversion rate is 99.0%.
Application example 5
In an anhydrous and anaerobic glove box, 50.6. 50.6 mg of the zirconium catalyst obtained in example 1 and 989.7 mg of L-lactide were weighed, mixed, heated to 100℃and reacted with stirring 2 h. After the reaction is finished, after the reaction system is restored to room temperature, dichloromethane is added to completely dissolve the crude product. The obtained solution was dropped into absolute ethanol, and a white solid was precipitated. Centrifuging to remove the solvent, and vacuum drying the obtained solid to obtain the poly L-lactide. The molecular weight of the obtained poly L-lactide was 16.1. 16.1 kg/mol, the molecular weight distribution was 1.20, and the monomer conversion was 99.1%.
Application example 6
The specific operation of this application example was the same as that of application example 5, except that the amount of L-lactide charged in the reaction was 1.0018 and g, and the amount of zirconium catalyst charged was 10.3 and mg. The molecular weight of the poly L-lactide obtained by the reaction is 30.2 kg/mol, the molecular weight distribution is 1.27, and the monomer conversion rate is 97.6%.
Application example 7
The specific operation of this application example was the same as that of application example 5, except that the charged amount of L-lactide in the reaction was 989.7 mg, the charged amount of zirconium catalyst was 25.2 mg, and the reaction time was 1 h. The molecular weight of the poly L-lactide obtained by the reaction is 17.5 kg/mol, the molecular weight distribution is 1.19, and the monomer conversion rate is 95.5%.
Application example 8
The specific operation of this application example was the same as that of application example 5, except that the reaction temperature was 180℃and the reaction time was 1 h in the course of the reaction. The molecular weight of the poly L-lactide obtained by the reaction is 15.9 kg/mol, the molecular weight distribution is 1.34, and the monomer conversion rate is 98.0%.
Application example 9
In an anhydrous and anaerobic glove box, 25.0 of the zirconium catalyst obtained in example mg, 494.5 mg of L-lactide and 396.8 mg epsilon-caprolactone were weighed, mixed, heated to 100℃and reacted under stirring for 2 h. After the reaction is finished, after the reaction system is restored to room temperature, dichloromethane is added to completely dissolve the crude product. The obtained solution was dropped into absolute ethanol, and a white solid was precipitated. Centrifuging to remove the solvent, and vacuum drying the obtained solid to obtain the L-lactide-epsilon-caprolactone copolymer. The molecular weight of the resulting copolymer was 14.1. 14.1 kg/mol and the molecular weight distribution was 1.23.
Application example 10
In an anhydrous and anaerobic glove box, 25.1 and mg of the zirconium catalyst obtained in example 1 and 989.6 mg of D, L-lactide were weighed, mixed, heated to 130℃and reacted with stirring 2 h. After the reaction is finished, after the reaction system is restored to room temperature, dichloromethane is added to completely dissolve the crude product. The obtained solution was dropped into absolute ethanol, and a white solid was precipitated. Centrifuging to remove the solvent, and vacuum drying the obtained solid to obtain the poly D, L-lactide. The obtained poly D, L-lactide had a molecular weight of 21.5 kg/mol, a molecular weight distribution of 1.43 and a monomer conversion of 98.4%.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (10)

1. An organometallic catalyst based on a tetradentate nitroxide ligand, characterized in that the catalyst is a complex having an N, N' -bis (3, 5-di-tert-butylsalicylidene) ethylenediamine structure, and has a chemical structural formula:
2. a method for preparing the organometallic catalyst according to claim 1, comprising the steps of:
(1) Under anhydrous and anaerobic conditions, respectively dissolving a ligand N, N '-bis (3, 5-di-tert-butylsalicylidene) ethylenediamine and zirconium tert-butoxide by using a certain amount of solvent, dropwise adding a zirconium tert-butoxide solution into the N, N' -bis (3, 5-di-tert-butylsalicylidene) ethylenediamine solution under stirring, and reacting for a period of time at a certain temperature;
(2) And after the reaction is finished, removing the solvent, and recrystallizing the crude product to obtain the organic metal catalyst.
3. The process according to claim 2, wherein the molar ratio of N, N' -bis (3, 5-di-t-butylsalicylidene) ethylenediamine to zirconium t-butoxide used in step (1) is 1:1 to 1:2;
the chemical structural formula of the N, N' -bis (3, 5-di-tert-butylsalicylidene) ethylenediamine is as follows:
4. the method according to claim 2, wherein in the step (1), the zirconium tert-butoxide solution is dropped into the N, N' -bis (3, 5-di-tert-butylsalicylidene) ethylenediamine solution at-20 to 25 ℃.
5. The preparation method according to claim 2, wherein in the step (1), the solvent is selected from one or more of benzene, toluene, anhydrous diethyl ether and dichloromethane, and the mass of the solvent is 5-40 times of the total mass of the reaction raw materials.
6. The method according to claim 2, wherein the reaction in step (1) is started after the reaction system is returned to room temperature, the reaction temperature is 25-80 ℃ and the time is 2 h-24 h.
7. The method according to claim 2, wherein the recrystallization solvent in the step (2) is one or more of benzene, toluene, xylene, trimethylbenzene, petroleum ether, n-hexane, and cyclohexane.
8. Use of an organometallic catalyst according to claim 1 for catalyzing the ring-opening polymerization of cyclic lactones, characterized in that it comprises the steps of:
step one: weighing a certain amount of cyclic lactone monomer and the organic metal catalyst in a glove box without water and oxygen;
step two: in a glove box without water and oxygen, reacting a monomer and an organic metal catalyst for a period of time at a certain temperature;
step three: after the reaction system is cooled to room temperature, transferring the reaction system to the outside of a glove box, adding a proper amount of good solvent to completely dissolve the reactant, then dripping the obtained solution into the poor solvent, precipitating the polymer, centrifuging to remove the solvent, taking the precipitate, and drying under vacuum to obtain the cyclic lactone polymer.
9. The use according to claim 8, wherein in step one the cyclic lactone monomer is any one or more of L-lactide, D, L-lactide, epsilon-caprolactone; the molar ratio of the monomer to the organometallic catalyst is from 100:1 to 630:1.
10. The use according to claim 8, wherein in step two the reaction temperature is 40 ℃ to 180 ℃ and the reaction time is 0.5 h to 8 h; in the third step, the good solvent is any one or more of benzene, toluene, xylene, trimethylbenzene, tetrahydrofuran, dichloromethane, dichloroethane, chloroform and hexafluoroisopropanol; the poor solvent is one or more of methanol, ethanol, diethyl ether, petroleum ether and n-hexane.
CN202410025420.9A 2024-01-08 2024-01-08 Organometallic catalyst based on tetradentate nitroxide ligand and preparation method and application thereof Pending CN117865998A (en)

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