CN112079999B - Method for catalyzing ring opening polymerization of cyclic ester by zinc catalyst - Google Patents
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Abstract
The invention discloses a method for catalyzing ring-opening polymerization of cyclic ester by a zinc catalyst, belonging to the technical field of polymer synthetic materials. The invention solves the problems that the existing zinc catalyst for catalyzing the ring opening of cyclic ester needs to support the participation of ligand, and the reaction activity and controllability are improved by changing the steric hindrance and the electrical property of central metal. In the invention, under the catalysis of a bis (hexa-alkyl disilyl nitrogen alkyl) zinc catalyst, an alcohol compound initiates lactone to carry out ring-opening polymerization reaction, so as to obtain a polyester material with a rich structure. The catalyst adopted by the invention is a bis (hexa-alkyl disilyl nitrogen alkane) zinc catalyst which is green and environment-friendly and does not need ligand participation, can realize high-efficiency high-controllable activity polymerization of different lactones under mild conditions, and has good monomer universality, thereby obtaining various polyester materials with different structures. The system has good universality for ring-opening polymerization of cyclic ester monomers, can catalyze and synthesize various degradable polyester materials, and promotes the development of sustainable polymers.
Description
Technical Field
The invention relates to a method for catalyzing ring-opening polymerization of cyclic ester by a zinc catalyst, belonging to the technical field of polymer synthetic materials.
Background
In recent years, with the shortage of petroleum resources, the increase of white pollution caused by waste plastics and the increasing of environmental awareness, sustainable polymers with green sources and degradable performances are widely researched. Aliphatic polyester is a typical sustainable polymer, and has been widely used in the fields of food packaging, medical devices, medical polymers, and the like due to its excellent biocompatibility, biodegradability, and mechanical properties comparable to those of conventional petroleum-based polymers, and thus has received increasing attention.
For the research on the synthesis of aliphatic polyester, dicarboxylic acid and derivatives thereof and dihydric alcohol are mainly prepared by a condensation polymerization method in the early stage, but by a polycondensation method, low-molecular-weight or multi-branched by-products exist in the reaction, so that a polyester material with higher molecular weight is difficult to obtain, the molecular weight distribution is wide and difficult to control, and the mechanical properties of the obtained material are limited; and the reaction usually needs high temperature, the conditions are harsh, the reaction activity is low, the reaction time is long, and the reaction difficulty and the cost are increased. In recent years, polyester materials are obtained by ring-opening polymerization of cyclic esters through metal coordination catalysis, and the polyester materials are greatly developed at present because of the advantages of mild reaction conditions, high monomer conversion rate, high molecular weight of the obtained polymers, controllable molecular weight and molecular weight distribution of the polymers and the like.
Only stannous octoate can successfully realize industrial application of the developed cyclic ester coordination polymerization catalyst at present, but the inherent toxicity of metallic tin limits the application of the metallic tin in the fields of biological medicine and the like, so that the development of the environment-friendly metallic catalyst and the realization of the production of polyester by a green and environment-friendly process have important significance for green chemistry. The zinc metal is one of trace elements of human body, has the advantages of low price, no toxicity, no color and the like, and has good development prospect. However, most of the zinc catalysts reported at present need to support the participation of ligands, and the reaction activity and controllability are improved by changing the steric hindrance and the electrical property of the central metal. For example, the Mehrkhodavandi group of subjects realizes the high-activity polymerization of lactide by introducing secondary amine or imine coordination metal zinc to improve the catalytic activity (Inorg. chem., 2016, 55, 9445-9453); garden achieves highly efficient and controlled polymerization of lactide, caprolactone and beta-butyrolactone by introducing an aminophenol ligand (Macromolecules, 2020, 53, 4294-. The preparation of the ligand improves the preparation cost of the catalyst and reduces the production and application value of the catalyst.
Therefore, the method for preparing the polyester material by developing a novel method which is environment-friendly, simple and efficient, realizes the high-activity and high-controllability polymerization of the lactone, and has important significance for promoting the development of sustainable polymers. Therefore, it is necessary to provide a method for catalyzing ring-opening polymerization of cyclic ester by using zinc catalyst.
Disclosure of Invention
The invention provides a method for catalyzing ring-opening polymerization of cyclic ester by using a zinc catalyst, aiming at the problems that the existing zinc catalyst for catalyzing ring-opening of cyclic ester needs to support participation of a ligand and reaction activity and controllability are improved by changing steric hindrance and electric property of central metal.
A method for catalyzing ring-opening polymerization of cyclic ester by a zinc catalyst comprises the following steps:
under the conditions of normal pressure and inert gas protection, cyclic ester monomers are used as polymerization monomers, and the ring-opening polymerization reaction of cyclic lactone is initiated by alcohol compounds under the catalysis of a bis (hexaalkyl disilylazalane) zinc catalyst in an organic solvent or by adopting solvent-free polymerization.
Further, when ring-opening polymerization reaction is carried out in the presence of an organic solvent, the molar ratio of the cyclic ester monomer to the catalyst to the alcohol compound is (5000-20): 1: (1-500), the reaction temperature of the ring-opening polymerization reaction is-20 ℃ to 100 ℃, the reaction time is 1min to 24h, and the concentration of the cyclic ester monomer is 0.1mol/L to 8 mol/L.
Further, when ring-opening polymerization reaction is carried out under the solvent-free condition, the molar ratio of the cyclic ester monomer to the catalyst to the alcohol compound is (5000-20): 1: (1-500), the reaction temperature of the ring-opening polymerization reaction is 0-200 ℃, and the reaction time is 1 min-96 h.
Further, the molecular formula of the bis (hexaalkyldisilazane) zinc catalyst is Zn [ N (SiR)3)2]2The structural formula is as follows:
wherein R is an alkyl group, preferably R is a methyl group.
Further, the cyclic ester monomer structure is:
Further, the alcohol compound is an alcohol having 1 to 50 carbon atoms.
Further, the alcohol compound is one or more of methanol, ethanol, isopropanol, butanol, tert-butanol, benzyl alcohol and phenylpropanol which are mixed according to any proportion.
Still further, the alcohol compound is benzyl alcohol.
Further, the organic solvent is one or more of benzene, toluene, xylene, dichloromethane and tetrahydrofuran which are mixed according to any proportion.
The invention has the following beneficial effects: the catalyst adopted by the invention is a bis (hexa-alkyl disilyl nitrogen alkane) zinc catalyst which is green and environment-friendly and does not need ligand participation, can realize high-efficiency high-controllable activity polymerization of different lactones under mild conditions, and has good monomer universality, thereby obtaining various polyester materials with different structures. The invention also has the following effects:
(1) the zinc catalyst adopted by the invention catalyzes the ring-opening polymerization of cyclic ester, and the metal zinc is nontoxic, colorless, cheap and easily available, is one of trace elements of human body, has good biocompatibility, ensures that the polymerization process is more environment-friendly, reduces the environmental pollution, and simultaneously the synthesized polyester material has less biotoxicity, so that the polyester material has wider application prospect in the fields of biological medicine and the like;
(2) the zinc metal catalyst adopted by the invention does not need the participation of the ligand, reduces the cost and energy consumption required by the ligand synthesis process, and better accords with the principle of green development;
(3) the catalyst adopted by the invention catalyzes the ring-opening polymerization of the lactone, the reaction can be carried out efficiently under mild conditions, the activity is controllable, the method has the characteristic of active polymerization, the molecular weight and the molecular weight distribution of the obtained polymer can be accurately controlled, and the regulation and control of thousands to hundreds of thousands of molecular weights can be realized by adjusting the equivalent ratio of the monomer to the initiator, so as to obtain the high-molecular-weight polyester material;
(4) the catalyst adopted by the invention has good universality for ring-opening polymerization of cyclic ester monomers, has good catalytic polymerization effect for various cyclic ester monomers with different structures, and can obtain polyester materials with different structures and performances.
Drawings
FIG. 1 is a graph of molecular weight versus degree of polymerization for polylactide of example 2;
FIG. 2 is a 1H NMR chart of a polymer obtained by polymerization of β -butyrolactone in example 7;
FIG. 3 is a 1H NMR chart of a polymer obtained by polymerization of delta valerolactone in example 8.
Detailed Description
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
Example 1: catalyzing the ring opening polymerization of the racemic lactide under different addition amounts of the alcohol initiator.
1. A5 mL Schlenk flask was charged, evacuated and replaced with argon, and then 3.86mg (10. mu. mol, 1eq.) of Zn [ N (SiMe.) was added to the flask3)2]2The catalyst was dissolved in 1mL of solvent, and then a 1mol/L toluene solution of benzyl alcohol with different equivalents was added and stirred for five minutes. Then 144mg (1mmol, 100eq.) of racemic lactide monomer was added and the reaction was stirred at room temperature.
2. After the reaction was completed, the reaction was quenched with benzoic acid. Nuclear magnetic measurement of reaction conversion. The solvent was removed in vacuo, the polymer isolated by washing with ice methanol and dried in vacuo to constant weight. The molecular weight (Mn) and the molecular weight distribution (PDI) of the resulting polymer were measured by Gel Permeation Chromatography (GPC), and the isotacticity was calculated by nuclear-decoupled nuclear magnetic resonance spectroscopy, and the results are shown in table 1 below:
TABLE 1 Ring opening polymerization of racemic lactide at different alcohol initiator addition levels
Table 1 shows the results of ring-opening polymerization of racemic lactide at different alcohol initiator addition levels. Group 1 is that when no benzyl alcohol initiator was added, the polymerization did not proceed smoothly. Group 2 is that when 1 equivalent of benzyl alcohol was added, the reaction reached 74% conversion in 30 minutes, but the molecular weight distribution was broad and the reaction controllability was poor. Group 3 is that when two equivalents of benzyl alcohol are added, high activity polymerization of racemic lactide can be achieved, 96% conversion rate can be obtained within 3 minutes, molecular weight distribution is significantly narrowed, and controllability of polymerization is improved. Group 4 is that when four equivalents of benzyl alcohol are added, the controllability of the reaction is further improved, the molecular weight more conforms to the theoretical value, and the molecular weight distribution is narrower. The reaction solvent was changed to toluene (group 5), the reaction still had good activity and controllability.
Example 2: the ethyl lactate initiates the ring-opening polymerization of the racemic lactide.
1. A5 mL Schlenk flask was charged, evacuated and replaced with argon, and then 3.86mg (10. mu. mol, 1eq.) of Zn [ N (SiMe.) was added to the flask3)2]2The catalyst was dissolved in 1mL of a toluene solvent, and then 40. mu.L of a 1mol/L toluene solution of ethyl lactate was added thereto, followed by stirring for five minutes. Then 144mg (1mmol, 100eq.) of racemic lactide monomer was added and the reaction was stirred at room temperature.
2. After 8 minutes of reaction, the reaction was quenched with benzoic acid. The reaction conversion was 97% by nuclear magnetic assay. The solvent was removed in vacuo, the polymer isolated by washing with ice methanol and dried in vacuo to constant weight. The polymer obtained had a molecular weight (Mn) of 9400g/mol and a molecular weight distribution (PDI) of 1.26 as determined by Gel Permeation Chromatography (GPC), and an isotacticity of 0.62 as calculated from a homonuclear decoupled nuclear magnetic resonance spectrum.
Example 3: catalyzing the ring opening polymerization of the racemic lactide under different monomer equivalent weights.
1. A10 mL Schlenk flask was evacuated and replaced with argon, and then 3.86mg (10. mu. mol, 1eq.) of Zn [ N (SiMe.) was added to the flask3)2]2The catalyst was dissolved in 1mL of methylene chloride solvent, and then 20. mu.L of benzyl alcohol in 1mol/L toluene was added thereto, followed by stirring for five minutes. Then adding racemic lactide monomers with different equivalent ratios, controlling the monomer concentration to be 1mol/L, adding a solvent to dissolve the monomers, and stirring at room temperature for reaction.
2. After the reaction was completed, the reaction was quenched with benzoic acid. Nuclear magnetic measurement of reaction conversion. The solvent was removed in vacuo, the polymer isolated by washing with ice methanol and dried in vacuo to constant weight. The molecular weight (Mn) and the molecular weight distribution (PDI) of the resulting polymer were measured by Gel Permeation Chromatography (GPC), and the isotacticity was calculated by nuclear-decoupled nuclear magnetic resonance spectroscopy, and the results are shown in table 2 below:
TABLE 2 Ring opening polymerization of racemic lactide at different monomer equivalent ratios
The ring opening polymerization of racemic lactide at different monomer equivalent ratios is given in table 2. The molecular weight of the obtained polymer is increased proportionally with the increase of the equivalent ratio of the monomers, the relationship between the molecular weight of the polymer and the polymerization degree is shown in the third graph, the third graph shows that the polymer has excellent linear relationship, the reaction has the characteristic of living polymerization, and the polylactide with different molecular weights can be obtained by adjusting the equivalent ratio of the monomers.
Example 4: catalyzing the solvent-free polymerization of racemic lactide.
1. A5 mL Schlenk flask was evacuated and replaced with argon, and then 1.93mg (5. mu. mol, 1eq.) of Zn [ N (SiMe.) was added to the flask3)2]2The catalyst was dissolved in 0.25mL of toluene, and then 20. mu.L of a 1mol/L solution of benzyl alcohol in toluene was added thereto, followed by stirring for five minutes. 1440mg (10mmol, 2000eq.) of racemic lactide monomer was then added and reacted at 130 ℃.
2. After 60 minutes of reaction, the reaction was quenched with benzoic acid. The reaction conversion was 88% by nuclear magnetic assay. The molecular weight (Mn) of the obtained polymer was 110500g/mol and the molecular weight distribution (PDI) was 1.54 as measured by Gel Permeation Chromatography (GPC), and the isotacticity was 0.58 as calculated from a homonuclear decoupled nuclear magnetic resonance spectrum.
The following examples 5 to 6 provide for the catalytic ring opening polymerization of optically pure lactide monomer to obtain polylactide.
Example 5: catalyzing the ring-opening polymerization of D-lactide.
1. A10 mL Schlenk flask was evacuated and replaced with argon, and then 3.86mg (10. mu. mol, 1eq.) of Zn [ N (SiMe.) was added to the flask3)2]2The catalyst was dissolved in 5mL of methylene chloride solvent, and then 20. mu.L of benzyl alcohol in 1mol/L toluene was added thereto, followed by stirring for five minutes. 720mg (1mmol, 500 eq) are then addedThe reaction was stirred at room temperature with D-lactide monomer.
2. After 45 minutes of reaction, the reaction was quenched with benzoic acid. The reaction conversion was 90% by nuclear magnetic measurement. The solvent was removed in vacuo, the polymer isolated by washing with ice methanol and dried in vacuo to constant weight. The polymer obtained had a molecular weight (Mn) of 43300g/mol and a molecular weight distribution (PDI) of 1.11 as determined by Gel Permeation Chromatography (GPC), and an isotacticity of greater than 0.99 as calculated by nuclear-decoupled nuclear magnetic resonance spectroscopy.
Example 6: catalyzing the ring-opening polymerization of L-lactide.
1. A10 mL Schlenk flask was evacuated and replaced with argon, and then 3.86mg (10. mu. mol, 1eq.) of Zn [ N (SiMe.) was added to the flask3)2]2The catalyst was dissolved in 5mL of methylene chloride solvent, and then 20. mu.L of benzyl alcohol in 1mol/L toluene was added thereto, followed by stirring for five minutes. 720mg (1mmol, 500eq.) of L-lactide monomer was then added and the reaction stirred at room temperature.
2. After 45 minutes of reaction, the reaction was quenched with benzoic acid. The reaction conversion was 88% by nuclear magnetic assay. The solvent was removed in vacuo, the polymer isolated by washing with ice methanol and dried in vacuo to constant weight. The polymer obtained had a molecular weight (Mn) of 39500g/mol and a molecular weight distribution (PDI) of 1.09 by Gel Permeation Chromatography (GPC), and an isotacticity of greater than 0.99 was calculated by nuclear magnetic resonance spectroscopy (NMR).
In this example, for the ring-opening polymerization of optically pure lactide, the isotacticity of the resulting polymer was greater than 0.99, indicating that there were fewer side reactions of racemization during the polymerization, and an optically pure polymer could be obtained by this catalytic system.
Example 7: catalytic ring-opening polymerization of monomer beta-butyrolactone
1. A5 mL Schlenk flask was charged, evacuated and replaced with argon, and then 3.86mg (10. mu. mol, 1eq.) of Zn [ N (SiMe.) was added to the flask3)2]2The catalyst was dissolved in 1mL of a toluene solvent, and then 20. mu.L of a 1mol/L toluene solution of benzyl alcohol was added thereto, followed by stirring for five minutes. Then 86mg (1mmol, 100eq.) of β -butyrolactone monomer was added, the reaction tube was removed from the glove box and the reaction stirred at 60 ℃.
2. After 240 minutes of reaction, the reaction was quenched with benzoic acid. The reaction conversion was 80% by nuclear magnetic measurement. The solvent was removed in vacuo, the polymer isolated by washing with ice methanol and dried in vacuo to constant weight. The polymer obtained had a molecular weight (Mn) of 5400g/mol and a molecular weight distribution (PDI) of 1.16 as determined by Gel Permeation Chromatography (GPC).
In this example, polyhydroxybutyric acid was obtained by ring-opening polymerization of β -butyrolactone. FIG. 1 shows the nuclear magnetic spectrum of the polymer, and it can be seen from the spectrum that the polymerization is initiated by benzyl alcohol and has benzyl alcohol chain ends. The absence of significant crotonate chain ends on the nuclear magnetic spectrum indicates that chain end dehydration has fewer elimination side reactions during the catalytic polymerization.
Example 8: catalytic ring-opening polymerization of monomer delta-valerolactone
1. A5 mL Schlenk flask was charged, evacuated and replaced with argon, and then 3.86mg (10. mu. mol, 1eq.) of Zn [ N (SiMe.) was added to the flask3)2]2The catalyst was dissolved in 1mL of a toluene solvent, and then 20. mu.L of a 1mol/L toluene solution of benzyl alcohol was added thereto, followed by stirring for five minutes. Then 100mg (1mmol, 100eq.) of delta-valerolactone monomer was added and the reaction was stirred at room temperature.
2. After 1 minute of reaction, the reaction was quenched with benzoic acid. The reaction conversion was 91% by nuclear magnetic assay. The solvent was removed in vacuo, the polymer isolated by washing with ice methanol and dried in vacuo to constant weight. The polymer obtained had a molecular weight (Mn) of 7400g/mol and a molecular weight distribution (PDI) of 1.22 as determined by Gel Permeation Chromatography (GPC).
In this example, the polyglutarilactone is obtained by ring-opening polymerization of delta-valerolactone. The polymerization has high activity and controllability. FIG. 2 shows the nuclear magnetic spectrum of the polymer with a well-defined benzyl alcohol chain end.
Example 9: catalyzing the ring opening polymerization of the monomer epsilon-caprolactone.
1. A5 mL Schlenk flask was charged, evacuated and replaced with argon, and then 3.86mg (10. mu. mol, 1eq.) of Zn [ N (SiMe.) was added to the flask3)2]2The catalyst was dissolved in 1mL of a toluene solvent, and then 20. mu.L of a 1mol/L toluene solution of benzyl alcohol was added thereto, followed by stirring for five minutes. 114mg (1mmol, 100eq.) of epsilon-caprolactone monomer was then added, chamberThe reaction was stirred gently.
2. After 1 minute of reaction, the reaction was quenched with benzoic acid. The reaction conversion was 95% by nuclear magnetic measurement. The solvent was removed in vacuo, the polymer isolated by washing with ice methanol and dried in vacuo to constant weight. The polymer obtained had a molecular weight (Mn) of 8300g/mol and a molecular weight distribution (PDI) of 1.16 as determined by Gel Permeation Chromatography (GPC).
In this example, polycaprolactone was obtained by ring-opening polymerization of epsilon-caprolactone. The polymerization has high activity and controllability.
Example 10: catalyzing the ring opening polymerization of monomer ethyl glycolide.
1. A5 mL Schlenk flask was charged, evacuated and replaced with argon, and then 3.86mg (10. mu. mol, 1eq.) of Zn [ N (SiMe.) was added to the flask3)2]2The catalyst was dissolved in 1mL of methylene chloride solvent, and then 20. mu.L of benzyl alcohol in 1mol/L toluene was added thereto, followed by stirring for five minutes. Then 86mg (0.5mmol, 50eq.) of ethyl glycolide monomer was added and the reaction was stirred at room temperature.
2. After 2 minutes of reaction, the reaction was quenched with benzoic acid. The reaction conversion was 95% by nuclear magnetic measurement. The solvent was removed in vacuo, the polymer isolated by washing with ice methanol and dried in vacuo to constant weight. The polymer obtained had a molecular weight (Mn) of 17000g/mol and a molecular weight distribution (PDI) of 1.26 as determined by Gel Permeation Chromatography (GPC).
Example 11: catalyzing the ring opening polymerization of the monomer benzyl glycolide.
1. A5 mL Schlenk flask was charged, evacuated and replaced with argon, and then 3.86mg (10. mu. mol, 1eq.) of Zn [ N (SiMe.) was added to the flask3)2]2The catalyst was dissolved in 1mL of methylene chloride solvent, and then 20. mu.L of benzyl alcohol in 1mol/L toluene was added thereto, followed by stirring for five minutes. Then 148mg (0.5mmol, 50eq.) of benzyl glycolide monomer was added and the reaction was stirred at room temperature.
2. After 30 minutes of reaction, the reaction was quenched with benzoic acid. The reaction conversion was 88% by nuclear magnetic assay. The solvent was removed in vacuo, the polymer isolated by washing with ice methanol and dried in vacuo to constant weight. The polymer obtained had a molecular weight (Mn) of 9200g/mol and a molecular weight distribution (PDI) of 1.22 as determined by Gel Permeation Chromatography (GPC).
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (3)
1. A method for catalyzing ring opening polymerization of cyclic ester by a zinc catalyst is characterized by comprising the following steps:
under the conditions of normal pressure and inert gas protection, taking a cyclic ester monomer as a polymerization monomer, polymerizing in an organic solvent, and initiating the cyclic ester to carry out ring-opening polymerization reaction by an alcohol compound under the catalysis of a bis (hexamethyldisilazane) zinc catalyst;
the alcohol compound is benzyl alcohol;
the ring-opening polymerization reaction is polymerized under the condition of an organic solvent, and the molar ratio of the cyclic ester monomer to the catalyst to the alcohol compound is 100: 1: (2-4), the reaction temperature of the ring-opening polymerization reaction is room temperature, the reaction time is 3min, and the concentration of the cyclic ester monomer is 0.1 mol/L.
2. The method of claim 1, wherein the cyclic ester monomer structure is:
3. The method for catalyzing ring-opening polymerization of cyclic ester by using zinc catalyst as claimed in claim 1, wherein the organic solvent is one or more of benzene, toluene, xylene, dichloromethane and tetrahydrofuran, and the mixture is prepared by mixing the organic solvent and the toluene, the xylene, the dichloromethane and the tetrahydrofuran in any proportion.
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| CN113173856A (en) * | 2021-03-29 | 2021-07-27 | 中国科学院青岛生物能源与过程研究所 | Method for catalytic degradation of waste polyester material by using zinc catalyst |
| CN115368546B (en) * | 2021-05-19 | 2023-10-24 | 北京服装学院 | Preparation method of biodegradable polyester |
| CN113698584B (en) * | 2021-09-08 | 2023-08-18 | 中国科学院青岛生物能源与过程研究所 | Method for catalyzing ring-opening polymerization of lactide and analogue thereof by using magnesium catalytic system |
| CN114230772B (en) * | 2021-12-20 | 2023-07-07 | 内蒙古久泰新材料有限公司 | Nonmetallic catalyst for ring-opening polymerization of cyclic ester and application thereof |
| CN114195999B (en) * | 2021-12-31 | 2023-08-01 | 深圳市鑫元素新材料科技有限公司 | Preparation method of polylactone |
| CN114349941B (en) * | 2022-01-10 | 2023-08-11 | 万华化学集团股份有限公司 | Double amino metal catalyst and preparation method and application thereof |
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| WO2016117473A1 (en) * | 2015-01-19 | 2016-07-28 | 日本曹達株式会社 | Method for producing polyester |
| CN104610538A (en) * | 2015-02-13 | 2015-05-13 | 苏州大学 | Biodegradable polymer with side chain containing dual-iodine functional group and application of biodegradable polymer |
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