CN109734880B - Method for catalyzing lactide polymerization by using binuclear chiral amine imine magnesium complex - Google Patents
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Abstract
The invention discloses a method for catalyzing lactide polymerization by using a binuclear chiral amine imine magnesium complex, which takes the binuclear chiral amine imine magnesium complex as a catalyst and takesLactide is used as a raw material, and the lactide is catalyzed to polymerize under the anhydrous oxygen-free condition and under the gas protection condition, so that polylactide is obtained; the catalyst is a binuclear chiral amine imine magnesium complex. The binuclear chiral amine imine magnesium complex which is researched and developed by self is used as the catalyst for lactide ring-opening polymerization reaction, the catalyst is simple in preparation method, low in cost, various in structure variation, high in catalytic activity, high in stereoselectivity, free of cocatalyst and high in reaction rate, and the metal central magnesium is coordinated with N and N atoms of the ligand, so that the catalyst is an ideal catalyst. The polylactide obtained by the reaction has narrow molecular weight distribution, controllable molecular weight and high yield, and particularly shows higher catalytic activity and stereoselectivity when catalyzing the polymerization of racemic lactide, and the stereoselectivity can reach the highestP m=0.84。
Description
Technical Field
The invention relates to a method for catalyzing lactide polymerization, in particular to a method for catalyzing lactide 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. The excellent biocompatibility, biodegradability and sustainable development and utilization performance of the polylactide make the polylactide become the most promising polymer material in the 21 st century. The lactide monomer raw material is derived from renewable resources, and the polymer is biodegradable and environment-friendly, so that the lactide monomer raw material is generally concerned as a novel bio-based material.
Lactide ring-opening polymerization can prepare high molecular weight polymer, 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 which still needs to be solved is that it is difficult to avoid metal residues in the products produced from the metal complex catalysts, and it is almost impossible to completely remove these residues from the polymer, so that low-toxicity magnesium complexes become more promising catalysts, and such catalysts are more important particularly when the polymers are applied to the biomedical field.
Patent No. cn201310124575.x discloses a N, N-dimethylaniline-alcohol based magnesium catalyst which still needs benzyl alcohol as a cocatalyst and has the highest stereoselectivity Pr = 0.79 in catalyzing lactide polymerization.
Therefore, it is necessary to research new magnesium catalyst with good performance and low toxicity.
Disclosure of Invention
The invention provides a method for catalyzing lactide polymerization by using a binuclear chiral amine imine magnesium complex, which is simple to operate, takes a self-developed binuclear chiral amine imine magnesium complex as a catalyst, has good reaction controllability, high catalytic activity and high stereoselectivity of the catalyst, and the obtained polylactide has narrow molecular weight distribution, controllable molecular weight and high yield.
The technical scheme of the invention is as follows:
the invention provides a catalyst with good catalytic performance for lactide ring-opening polymerization, which is a binuclear chiral amine imine magnesium complex with a special structure, and the structural formula of the catalyst is shown as the following formula (I), wherein R is hydrogen, methyl, ethyl or isopropyl, preferably isopropyl, and OBn is benzyloxy:
the binuclear chiral amine imine magnesium compound 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 introduction of a bulky, sterically hindered substituent can reduce the catalytic activity of the catalyst, but increases the selectivity, so R is preferably isopropyl.
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.
The invention provides a method for catalyzing lactide polymerization by using a binuclear chiral amine imine magnesium complex, which takes the binuclear chiral amine imine magnesium complex (magnesium complex for short, the same below) as a catalyst and lactide as a raw material to catalyze lactide polymerization under the conditions of no water, no oxygen and gas protection to obtain polylactide which is a homopolymer. The catalyst of the invention has the tendency of reducing catalytic activity and increasing stereoselectivity along with the increase of the steric hindrance of the substituent R.
Further, the lactide is racemic lactide, levo-lactideThe binuclear chiral amine imine magnesium complex is used as a catalyst for lactide ring-opening polymerization reaction, the polymer obtained by the reaction has narrow molecular mass distribution, controllable molecular weight and high yield, and especially when the binuclear chiral amine imine magnesium complex is used for catalyzing the polymerization of racemic lactide, the obtained isotactic polylactide has high regularity, high stereoselectivity is shown, and the stereoselectivity can reach the highest degreeP m = 0.84。
Further, the method comprises the following steps of mixing the binuclear chiral amine imine magnesium complex catalyst, toluene and lactide, carrying out ring-opening polymerization reaction under the conditions of no water and no oxygen and gas protection, and treating reactants after reaction to obtain the polylactide. The lactide can be levo-lactide, meso-lactide, racemic lactide.
Further, in the ring-opening polymerization reaction, the molar ratio of the lactide to the binuclear chiral amine imine magnesium complex 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, the concentration of lactide in toluene is 0.2 to 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 ℃. With the increase of the polymerization reaction temperature, the stereoselectivity of the catalyst tends to be reduced, the catalytic activity tends to be increased, and when the reaction temperature is 100 ℃, the stereoselectivity of the racemic lactide can be achieved when the catalyst is used for catalyzingP m= 0.60, stereoselectivity when catalyzing racemic lactide at 0 deg.CP m = 0.84。
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, methanol is added to purify the polylactide after the reaction, so as to obtain purified polylactide.
The binuclear chiral amine imine magnesium complex is used as a catalyst for lactide ring-opening polymerization, the preparation method of the binuclear chiral amine imine magnesium complex catalyst is simple, the cost is low, the post-reaction treatment is simple, 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, the stereoselectivity is high, a cocatalyst is not needed, and the reaction rate is high, so that the binuclear chiral amine imine magnesium complex catalyst is an ideal catalyst. The polylactide obtained by the reaction has narrow molecular weight distribution, controllable molecular weight and high yield, and particularly shows higher catalytic activity and stereoselectivity when catalyzing the polymerization of racemic lactide, and the stereoselectivity can reach the highestP m = 0.84。
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 weights of polylactide homopolymersM nTacticity of the polymer, determined by GPC (polystyrene as standard), (B)P m) Measured by homonuclear decoupled hydrogen spectroscopy, PDI being the molecular weight distribution, measured by GPC; 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: under nitrogen atmosphere5 mL of benzyl alcohol in tetrahydrofuran (2.0 mol/L) was slowly added dropwise at 10 ℃ to an equimolar amount of Mg (R: (R))nBu)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 polylactide homopolymers
Example 5
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, firstly adding 10 mu mol of catalyst (magnesium complex shown in formula I, R is hydrogen), 4 mL of toluene and 1000 mu mol of racemic lactide into an ampoule after being washed and baked by high-purity nitrogen gas, and then adding the mixture into a reactor at 20 mu moloC, reacting for 6 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 0.137 g of product with the yield of 95%,M n0.9 ten thousand, PDI 1.03,P m0.74 and TOF 950.
Example 6
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, firstly adding 10 mu mol of different catalysts (magnesium complex shown in formula I), 4 mL of toluene and 1000 mu mol of racemic lactide into an ampoule after being washed and baked by high-purity nitrogen gas, and then adding the mixture into a flask with the reactor at 0 mu moloC, 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 polylactide homopolymer.
The reaction conditions for the different catalysts are shown in table 1 below:
from the results in the table above, it can be seen that the catalyst in which the substituent R is isopropyl group has the highest stereoselectivity.
Example 7
The method comprises the steps of carrying out reaction under the protection of anhydrous oxygen-free inert gas, firstly adding 10 mu mol of catalyst (magnesium complex shown in formula I, R is isopropyl), 8mL of toluene and 2000 mu mol of racemic lactide into an ampoule which is washed and baked by high-purity nitrogen, then carrying out reaction at different temperatures, adding a small amount of water after reaction to terminate the reaction, carrying out precipitation and washing for a plurality of times by using methanol, and carrying out vacuum drying at room temperature to obtain the polylactide homopolymer.
The polylactide homopolymers obtained at different reaction temperatures and reaction times are shown in table 2 below:
as can be seen from the results of the above table, the reaction rate increases with increasing reaction temperature, but the stereoselectivity decreases.
Example 8
Reacting under the protection of anhydrous oxygen-free and inert gas, firstly adding 10 mu mol of catalyst (amine imine magnesium complex shown in formula I, R is hydrogen), toluene and levorotatory lactide into an ampoule after being washed and baked by high-purity nitrogen gas to ensure that the concentration of the levorotatory lactide in the toluene is 0.25mol/L, and then adding the mixture into a flask after being washed and baked by 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 polylactide homopolymer.
The reaction conditions for different amounts of levolactide are shown in table 3 below:
example 9
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, firstly adding 10 mu mol of catalyst (magnesium complex shown in formula I, R is isopropyl), 8mL of toluene and 2000 mu mol of left-handed lactide into an ampoule after being washed and baked by high-purity nitrogen gas, and then adding the catalyst into the ampoule70oC, reacting for 1.5 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 0.282 g of product with the yield of 98%,M n1.0 million, PDI 1.18, and TOF 7840.
Example 10
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, firstly adding 10 mu mol of catalyst (magnesium complex shown in formula I, R is hydrogen), 32mL of toluene and 8000 mu mol of meso-lactide into an ampoule after being washed and baked by high-purity nitrogen, and then adding 70 mu mol of meso-lactide into the ampouleoC, reacting for 21 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 1.14 g of product with the yield of 99 percent,M n6.2 million, PDI of 1.18, TOF of 2263.
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).
Polylactide was prepared according to the conditions of table 2 No. 2 of example 7 above, except that: the catalyst is the zinc complex, and the method comprises the following steps: adding 10 mu mol of catalyst, 8ml of toluene and 2000 mu mol of racemic lactide into the ampoule after being baked by using high-purity nitrogen gas washing, and then placing the ampoule in a container of 60 mu moloC, reacting for 2min, adding a small amount of water to stop the reaction after the reaction is finished, precipitating and washing the reaction for a plurality of times by using methanol, and drying the reaction in vacuum at room temperature to obtain 0.03g of polylactide with low yield. The zinc complex has little ability to catalyze the polymerization of lactide in the absence of benzyl alcohol.
Comparative example 2
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 of polylactide by using the zinc complex as a catalyst comprises the following steps: adding 10 mu mol of catalyst, 20 mu mol of benzyl alcohol, 8ml of toluene and 2000 mu mol of racemic lactide into an ampoule after being baked by using high-purity nitrogen gas washing, and then placing the ampoule in a container with 60 mu mol of catalyst, benzyl alcohol and racemic lactideoC, reacting for 8min, adding a small amount of water to terminate 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 0.22g of polylactide, wherein the yield is 76.4%, the molecular weight is 0.8 ten thousand, the PDI is 1.10, the TOF is 1146, the TOF value is obviously much smaller than that (5940) of the number 2 in the table 2, and the homonuclear decoupling hydrogen spectrum of the polymer shows that the zinc complex catalyst has no selectivity.
Claims (13)
1. A method for catalyzing lactide polymerization by using a binuclear chiral amine imine magnesium complex is characterized by comprising the following steps: taking a binuclear chiral amine imine magnesium complex as a catalyst, taking lactide as a raw material, and catalyzing lactide polymerization under the anhydrous, oxygen-free and gas protection conditions to obtain polylactide; 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 the formula I, R is isopropyl.
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 isopropyl.
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 6, 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. The method according to any of claims 1-8, characterized by comprising the steps of: mixing the binuclear chiral amine imine magnesium complex catalyst, toluene and lactide, carrying out ring-opening polymerization reaction under the conditions of no water and oxygen and gas protection, and treating reactants after the reaction to obtain polylactide.
11. The method according to any of claims 1-8, characterized by: during ring-opening polymerization reaction, the molar ratio of lactide to catalyst is 100-1000: 1; the lactide is racemic lactide, levo-lactide or meso-lactide.
12. The method of claim 9, further comprising: the concentration of lactide in toluene is 0.2-0.3 mol/L.
13. The method of claim 1, further comprising: during the ring-opening polymerization reaction, the reaction temperature is 0-100 ℃, and the reaction time is 1-60 minutes.
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