CN109679081B - Method for catalyzing caprolactone polymerization by using binuclear chiral amine imine magnesium complex - Google Patents
Method for catalyzing caprolactone polymerization by using binuclear chiral amine imine magnesium complex Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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Abstract
The invention discloses a method for catalyzing caprolactone polymerization by using a binuclear chiral amine imine magnesium complex, which takes the binuclear chiral amine imine magnesium complex as a catalyst,to be provided withεCaprolactone as raw material, catalyzing under anhydrous and oxygen-free condition and gas protectionεPolymerizing caprolactone to obtain polycaprolactone. The binuclear chiral amine imine magnesium complex catalyst is used as a catalyst for caprolactone ring-opening polymerization, the preparation method of the binuclear chiral amine imine magnesium complex catalyst is simple, the cost is low, the product yield is high, the catalyst structure is varied, metal central magnesium is coordinated with N and N atoms of a ligand, the catalytic activity is high, a cocatalyst is not needed, the reaction rate is high, the molecular weight distribution of the obtained polymer is narrow, the molecular weight is controllable, and the yield is high.
Description
Technical Field
The invention relates to a method for catalyzing caprolactone polymerization, in particular to a method for catalyzing caprolactone polymerization by using a binuclear chiral amine imine magnesium complex.
Background
With the enhancement of environmental awareness, the development of degradable biological materials capable of reducing environmental pollution is one of important research fields of polymer materials. Polylactone is a biodegradable green environment-friendly high polymer material, and is receiving more and more attention as a substitute of petroleum products. In a natural living environment, the waste polylactone material can be thoroughly decomposed into small molecules by microorganisms in soil. Because polyester is non-toxic, non-irritating, and has good biocompatibility, it is widely used in medical and environmental fields, such as surgical sutures, packaging, drug controlled release, and tissue engineering scaffolds, etc. Polycaprolactone has excellent biocompatibility, biodegradability and sustainable development and utilization performance, so that polycaprolactone becomes a polymer material with the greatest development prospect in the 21 st century. The caprolactone monomer raw material is derived from renewable resources, and the polymer is biodegradable and environment-friendly, so the caprolactone monomer raw material is generally concerned as a novel bio-based material.
The caprolactone ring-opening polymerization can prepare high molecular weight polymers, and the molecular weight can be controlled through activity controllable polymerization. In recent years, scholars at home and abroad make a great deal of research work from the aspects of reducing the preparation cost and low toxicity of the catalyst and improving the molecular weight and stability of the polymer, and develop a plurality of metal complex catalysts with excellent performance. However, a problem still to be solved is that the products obtained from the metal complex catalysts are inevitably accompanied by metal residues, and it is almost impossible to completely remove these residues from the polymers, so that low-toxicity magnesium complexes are more promising catalysts, and particularly when the polymers are applied to the biomedical field, such catalysts are more important. Due to the excellent catalytic performance of the binuclear metal catalyst, the research of a new binuclear magnesium catalyst with good performance and low toxicity is necessary for obtaining polycaprolactone with higher safety.
Disclosure of Invention
The invention provides a method for catalyzing caprolactone polymerization by using a binuclear chiral amine imine magnesium complex, which is simple to operate, good in reaction controllability by using a self-developed binuclear chiral amine imine magnesium complex as a catalyst, and narrow in molecular mass distribution, controllable in molecular weight and high in yield of the obtained polycaprolactone.
The technical scheme of the invention is as follows:
the invention provides a catalyst with good catalytic performanceεThe catalyst is a binuclear chiral amine imine magnesium complex with a special structure, and has a structural formula shown as the following formula (I), wherein R is hydrogen, methyl, ethyl or isopropyl, preferably hydrogen, and OBn is benzyloxy:
the binuclear chiral amine imine magnesium complex is a complex, is obtained by coordinating N and N atoms of a ligand with a metal magnesium center, and has excellent catalytic performance. The ligand structure of the complex is special, and the selection of the substituent group in the ligand has great influence on the catalytic performance of the magnesium complex as a caprolactone ring-opening polymerization catalyst. Wherein R is hydrogen, methyl, ethyl or isopropyl. Further, introduction of a substituent having a small steric hindrance increases the catalytic activity of the magnesium catalyst, and therefore R is preferably hydrogen.
The binuclear chiral amine imine magnesium complex is prepared from ligand Mg (I), Mg (II)nBu)2(di-n-butyl magnesium) and benzyl alcohol, and the preparation method comprises the following steps: di-n-butyl magnesium (Mg: (B))nBu)2) The hexane solution reacts with a tetrahydrofuran solution of benzyl alcohol at a temperature of-5 to-15 ℃, a toluene solution of a ligand A is added at the temperature after the reaction is completed, the temperature of the system naturally rises to room temperature after the addition is completed, then the system is heated, the temperature is controlled to be 40 to 60 ℃ for reaction, the solvent is recovered after the reaction, and the obtained solid is washed and dried to obtain the binuclear chiral amine imine magnesium complex shown in the formula I.
Further, the structural formula of the ligand A is shown as the following formula, R is hydrogen, methyl, ethyl or isopropyl, and R is preferably isopropyl. The preparation method of the ligand A is reported in the literature, and the specific synthetic method is referred to in the literature (Polyhedron 85 (2015) 537-542).
Further, ligand A, Mg (nBu)2The equation for the reaction with benzyl alcohol is as follows:
in the preparation method, the ligand A, the di-n-butyl magnesium and the benzyl alcohol react in a one-pot method. The molar ratio of the ligand A, the di-n-butyl magnesium and the benzyl alcohol is 1: 2: 2. the method comprises the steps of firstly reacting di-n-butyl magnesium with benzyl alcohol to form n-butyl benzyloxy magnesium, then reacting with the ligand A to form a final complex, easily solidifying the obtained complex in hexane, easily separating and purifying the complex from a solvent, simply post-treating a reaction liquid, and having high product yield which is over 80 percent. Tests prove that if di-n-butyl magnesium directly reacts with the ligand A, the product obtained by the reaction is oily, is not easy to separate from a solvent, and has high separation and purification difficulty and low yield.
In the preparation method, the whole reaction is carried out under the protection of inert gas or nitrogen.
In the preparation method, the reaction is naturally raised to room temperature and then raised to 40-60 DEGoC by reaction, e.g. 40oC、50oC、60oC, preferably 50 to 60oC. In the range of 40 to 60oC (preferably 50-60)oC) The reaction time is 1 to 12 hours, preferably 3 to 6 hours.
In the preparation method, the hexane, the tetrahydrofuran and the toluene are all solvents, and the solvents have the function of ensuring that all the raw materials are fully dissolved, so that all the raw materials are subjected to contact reaction in a homogeneous phase, and the dosage of the solvents can be adjusted according to actual conditions. Preferably, the total mass of the hexane, the tetrahydrofuran and the toluene is 5-10 times of the total mass of the di-n-butyl magnesium, the benzyl alcohol and the ligand A.
In the preparation method, after the reaction, the solvent is pumped out of the reaction liquid in vacuum, then the residual precipitate is washed by n-hexane, and finally the product is obtained after drying.
When the binuclear chiral amine imine magnesium complex is used as a catalyst for the ring-opening polymerization reaction of caprolactone, the catalytic activity tends to be reduced along with the increase of the steric hindrance of a substituent R.
The invention provides a method for catalyzing caprolactone polymerization by using binuclear chiral amine imine magnesium, which takes binuclear chiral amine imine magnesium complex as a catalyst and takesεCaprolactone as raw material, catalyzing under anhydrous and oxygen-free condition and gas protectionεPolymerizing caprolactone to obtain polycaprolactone as homopolymer. The catalyst of the invention has a tendency of reducing the catalytic activity with the increase of the steric hindrance of the substituent R.
Further, the method comprises the following steps of mixing the binuclear chiral amine imine magnesium complex catalyst, toluene andε-alreadyMixing lactones, carrying out ring-opening polymerization reaction under the conditions of no water and no oxygen and gas protection, and treating reactants after the reaction to obtain polycaprolactone.
Further, in the ring-opening polymerization reaction, the molar ratio of the caprolactone to the binuclear chiral amine imine magnesium catalyst is 100-1000: 1, e.g. 100: 1. 200:1, 400:1, 600: 1. 800:1 and 1000: 1.
Further, in the ring-opening polymerization reaction,εthe concentration of caprolactone in toluene is between 0.2 and 0.3 mol/L.
Further, in the ring-opening polymerization reaction, the polymerization reaction temperature is 0 to 100 ℃, for example, 0 ℃, 20 ℃, 40 ℃, 60 ℃, 80 ℃, 100 ℃. As the polymerization temperature increases, the catalytic activity tends to increase.
Further, in the ring-opening polymerization reaction, the polymerization reaction time is 1 to 60 minutes, for example, 1 minute, 10 minutes, 30 minutes, 40 minutes, 60 minutes, or the like.
Further, in the ring-opening polymerization reaction, the protective gas is an inert gas or nitrogen.
Further, in the ring-opening polymerization reaction, cold methanol is added after the reaction to purify polycaprolactone, so that purified polycaprolactone is obtained.
The binuclear chiral amine imine magnesium complex catalyst is used as a catalyst for caprolactone ring-opening polymerization, the preparation method of the binuclear chiral amine imine magnesium complex catalyst is simple, the cost is low, the product yield is high, the catalyst structure is varied, metal center magnesium is coordinated with N and N atoms of a ligand, the catalytic activity is high, a cocatalyst is not needed, the reaction rate is high, the molecular weight distribution of the obtained polymer is narrow, the molecular weight is controllable, the yield is high, and the market demand is met.
Detailed Description
The invention is further illustrated by the following specific examples, which are not intended to be limiting and whose scope is indicated in the claims.
In the examples below, the molecular weight of the polycaprolactone homopolymerM nMeasured by GPC (polystyrene as standard), PDI is molecular weight distribution, and measured by GPC(ii) a TOF is the amount of monomer catalyzed per unit of catalyst per unit of time.
Preparation of binuclear chiral amine imine magnesium complex (I) by using ligand A as raw material
The binuclear chiral amine imine magnesium complex shown in the formula (I) is composed of a ligand A, Mg (I)nBu)2And benzyl alcohol by alkyl elimination reaction, the reaction formula is as follows.
Example 1
The structural formula of the ligand is shown as the formula (A), wherein R is hydrogen, and the reaction process is as follows: 5 mL of benzyl alcohol in tetrahydrofuran (2.0 mol/L) was slowly added dropwise to an equimolar amount of Mg (R) at-10 ℃ under a nitrogen atmospherenBu)2Hexane solution (2.0 mol/L, 5 mL) was reacted for 1 hour, 2.14 g of ligand was dissolved in 25 mL of dry toluene, and added to Mg (at-10 ℃.) (nBu)2And benzyl alcohol, naturally heating the reaction solution to room temperature after adding the benzyl alcohol, heating the reaction solution to 60 ℃ for reaction for 3 hours, vacuumizing the solvent after the reaction is finished, adding dry n-hexane into the residue for washing, filtering, collecting the product, drying and weighing to obtain 3.05 g of solid, wherein the yield is 83.4%.
Example 2
The structural formula of the ligand is shown as the formula (A), wherein R is methyl, and the reaction process is as follows: 5 mL of benzyl alcohol in tetrahydrofuran (2.0 mol/L) was slowly added dropwise to an equimolar amount of Mg (R) at-10 ℃ under a nitrogen atmospherenBu)2Hexane solution (2.0 mol/L, 5 mL) was reacted for 1 hour, 2.64 g of ligand was dissolved in 25 mL of dry toluene, and added to Mg (at-10 ℃.) (nBu)2And benzyl alcohol, naturally heating the reaction solution to room temperature after adding the benzyl alcohol, heating the reaction solution to 40 ℃ for reaction for 10 hours, vacuumizing the solvent after the reaction is finished, adding dried n-hexane into the residue, washing, filtering, collecting the product, drying and weighing to obtain 3.33 g of solid with the yield of 84.5 percent.
Example 3
The structural formula of the ligand is shown as the formula (A), wherein R is ethyl, and the reaction process is as follows: 5 mL of benzyl alcohol in tetrahydrofuran (2.0 mol/L) was slowly added dropwise to an equimolar amount of Mg (R) at-10 ℃ under a nitrogen atmospherenBu)2Hexane solution (2.0 mol/L, 5 mL) was reacted for 1 hour, 2.92 g of ligand was dissolved in 30 mL of dry toluene, and added to Mg (10 ℃ C.) (nBu)2And benzyl alcohol, adding the mixture, naturally heating the reaction solution to room temperature, heating the reaction solution to 50 ℃ for reaction for 6 hours, after the reaction is finished, vacuumizing the reaction solution, adding dried n-hexane into the residue, filtering the residue, washing the residue with the dried n-hexane, filtering the filtrate, collecting the product, drying and weighing the product to obtain 3.66 g of solid with the yield of 86.6 percent.
Example 4
The structural formula of the ligand is shown as the formula (A), wherein R is isopropyl, and the reaction process is as follows: 5 mL of benzyl alcohol in tetrahydrofuran (2.0 mol/L) was slowly added dropwise to an equimolar amount of Mg (R) at-10 ℃ under a nitrogen atmospherenBu)2Hexane solution (2.0 mol/L, 5 mL) was reacted for 1 hour, 3.20 g of ligand was dissolved in 35 mL of dry toluene, and added to Mg (10 ℃ C.) (nBu)2And benzyl alcohol, adding the mixture, naturally heating the reaction solution to room temperature, heating the reaction solution to 50 ℃ for reaction for 10 hours, after the reaction is finished, vacuumizing the reaction solution, adding dried n-hexane into the residue, filtering the residue, washing the residue with the dried n-hexane, filtering the residue, collecting the product, drying and weighing the product to obtain 3.98 g of solid with the yield of 88.4 percent.
Preparation of polycaprolactone homopolymer
Example 5
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, and firstly sequentially adding 10 mu mol of catalyst (magnesium complex shown in formula I, R is hydrogen), 4 mL of toluene and 1000 mu mol of catalyst in an ampoule after being washed and baked by high-purity nitrogen gasεCaprolactone, then at 20oC, reacting for 1 minute, adding a small amount of water to terminate the reaction, precipitating with methanol, washing for several times, vacuum drying at room temperature to obtain 0.113 g of product with the yield of 99%,M n1.0 ten thousand, PDI 1.02, TOF 5940.
Example 6
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, and firstly sequentially adding 10 mu mol of different catalysts (magnesium complex shown in formula I), 4 mL of toluene and 1000 mu mol of catalyst into an ampoule after being washed and baked by high-purity nitrogen gasεCaprolactone, then at 0oC, reacting in ice bath, adding a small amount of water after the reaction to terminate the reaction, precipitating and washing for a plurality of times by using methanol, and drying in vacuum at room temperature to obtain the polycaprolactone homopolymer.
The reaction conditions for the different catalysts are shown in table 1 below:
from the results in the table, it can be seen that the catalyst with the substituent R as hydrogen has the highest catalytic activity and the fastest reaction speed.
Example 7
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, and firstly sequentially adding 10 mu mol of catalyst (magnesium complex shown in formula I, R is hydrogen), 8 mL of toluene and 2000 mu mol of catalyst into an ampoule after being washed and baked by high-purity nitrogen gasεCaprolactone, reacting at different temperatures, adding a small amount of water to terminate the reaction, precipitating with methanol, washing for several times, and vacuum drying at room temperature to obtain polycaprolactone homopolymer.
The polycaprolactone homopolymers obtained at different reaction temperatures and reaction times are shown in Table 2 below:
as can be seen from the above results, as the reaction temperature increases, the time required for polycaprolactone to reach a similar molecular weight decreases, and the reaction speed increases.
Example 8
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 10 mu mol of catalyst (a magnesium complex shown in formula I, R isHydrogen), toluene andεcaprolactone, toεThe concentrations of caprolactone in toluene were all 0.25mol/L and then 70 mol/LoAnd C, reacting, adding a small amount of water after the reaction to terminate the reaction, precipitating with methanol, washing for several times, and drying in vacuum at room temperature to obtain the polycaprolactone homopolymer.
Is differentεThe reaction behavior of the amounts of caprolactone used is shown in Table 3 below:
example 9
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, and firstly sequentially adding 10 mu mol of catalyst (a magnesium complex shown in formula I, R is isopropyl), 8 mL of toluene and 2000 mu mol of catalyst into an ampoule after being washed and baked by high-purity nitrogen gasεCaprolactone, then at 70oC, reacting for 1.2 minutes, adding a small amount of water to terminate the reaction, precipitating with methanol, washing for several times, vacuum drying at room temperature to obtain 0.226 g of product with the yield of 99 percent,M n2.0 ten thousand, PDI 1.18, TOF 9900.
Comparative example 1
A zinc complex having a structure represented by the following formula was synthesized by a method described in reference (Polyhedron 85 (2015) 537-542).
The preparation method of polycaprolactone by using the zinc complex as a catalyst comprises the following steps: carrying out reaction under the protection of anhydrous and oxygen-free inert gas, and firstly, sequentially adding 10 mu mol of catalyst, 8 mL of toluene and 2000 mu mol of catalyst into an ampoule after being washed and baked by high-purity nitrogen gasεCaprolactone, then placed at 70oC, reacting for 2min, adding a small amount of water to stop the reaction after the reaction is finished, precipitating and washing for a plurality of times by using methanol, and drying in vacuum at room temperature to obtain 0.02 g of poly-lactide with low yield. The zinc complexes hardly catalyze the polymerization of caprolactone in the absence of benzyl alcoholCapability.
Meanwhile, the zinc complex is used as a catalyst, benzyl alcohol is used as a cocatalyst to prepare polycaprolactone, and the preparation method comprises the following steps: carrying out reaction under the protection of anhydrous and anaerobic inert gases, and firstly, sequentially adding 10 mu mol of catalyst, 20 mu mol of benzyl alcohol, 8 mL of toluene and 2000 mu mol of catalyst into an ampoule after being washed and baked by high-purity nitrogen gasεCaprolactone, then placed at 70oC for 3.5min, adding a small amount of water to stop the reaction after the reaction is finished, precipitating and washing the reaction product for a plurality of times by using methanol, and drying the reaction product in vacuum at room temperature to obtain 0.21 g of the poly-lactide, wherein the yield is 92 percent, the molecular weight is 3.4 ten thousand, the TOF is 6446, and the TOF value is obviously much smaller than that (9900) of example 9.
Claims (13)
1. A method for catalyzing caprolactone polymerization by using a binuclear chiral amine imine magnesium complex is characterized by comprising the following steps: uses a binuclear chiral amine imine magnesium complex as a catalyst toεCaprolactone as raw material, catalyzing under anhydrous and oxygen-free condition and gas protectionεPolymerizing caprolactone to obtain polycaprolactone; the structural formula of the binuclear chiral amine imine magnesium complex is shown as the following formula I, wherein R is hydrogen, methyl, ethyl or isopropyl; OBn is benzyloxy;
2. the method of claim 1, further comprising: in formula I, R is hydrogen.
3. The method of claim 1, further comprising: the binuclear chiral amine imine magnesium complex is prepared by the following method: reacting a hexane solution of di-n-butylmagnesium with a tetrahydrofuran solution of benzyl alcohol at a temperature of between-5 and-15 ℃, adding a toluene solution of a ligand A at the temperature after the reaction is completed, naturally raising the temperature of the system to room temperature after the addition is completed, heating, controlling the temperature to be between 40 and 60 ℃ for reaction, recovering the solvent after the reaction, washing and drying the obtained solid to obtain the binuclear chiral amine imine magnesium complex shown in the formula I; the structural formula of the ligand A is shown as the following, wherein R is hydrogen, methyl, ethyl or isopropyl;
4. the method of claim 3, wherein: in the ligand A, R is hydrogen.
5. The method of claim 3, wherein: when the binuclear chiral amine imine magnesium complex is prepared, the molar ratio of the ligand A to the di-n-butyl magnesium to the benzyl alcohol is 1: 2: 2.
6. the method of claim 3, wherein: when the binuclear chiral amine imine magnesium complex is prepared, the temperature is controlled to be 50-60 DEGoAnd C, carrying out a reaction.
7. The method of claim 3, wherein: when the binuclear chiral amine imine magnesium complex is prepared, the concentration is 40-60%oThe reaction time of C is 1-12 hours.
8. The method of claim 7, wherein: when the binuclear chiral amine imine magnesium complex is prepared, the concentration is 40-60%oAnd C, the reaction time is 3-6 hours.
9. The method of claim 3, wherein: when the binuclear chiral amine imine magnesium complex is prepared, the reaction is carried out under the protection of inert gas or nitrogen.
10. A method according to any of claims 1-9, characterized by the steps of: the binuclear chiral amine imine magnesium complex catalyst, toluene andεmixing caprolactone, carrying out ring-opening polymerization reaction under the conditions of no water, no oxygen and gas protection, and treating reactants after the reaction to obtain polycaprolactone.
11. The method according to any of claims 1-9, characterized by: during ring-opening polymerization, the molar ratio of caprolactone to the catalyst is 100-1000: 1.
12. the method of claim 10, further comprising:εthe concentration of caprolactone in toluene is between 0.2 and 0.3 mol/L.
13. The method according to any of claims 1-9, characterized by: during the ring-opening polymerization reaction, the reaction temperature is 0-100 ℃, and the reaction time is 1-60 minutes.
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