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CN118184981A - Organometallic catalyst and preparation method and application thereof - Google Patents

Organometallic catalyst and preparation method and application thereof Download PDF

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Publication number
CN118184981A
CN118184981A CN202211598856.4A CN202211598856A CN118184981A CN 118184981 A CN118184981 A CN 118184981A CN 202211598856 A CN202211598856 A CN 202211598856A CN 118184981 A CN118184981 A CN 118184981A
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organometallic catalyst
substituted
ion
polydioxanone
catalyst
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朱德兆
罗琛
董玥
董霄
李阳
李锦山
杨延翔
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Petrochina Co Ltd
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/025—Silicon compounds without C-silicon linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyethers (AREA)

Abstract

The invention provides an organic metal catalyst which has a structure shown in a formula I, wherein M is a divalent metal ion; r 1 is a linear or branched alkyl group; r 2 is a linear or branched alkyl group, n=0, 1, 2 or 3; x is selected from N, O, S, P, when X is selected from N or P, X and R 1 are connected through a covalent bond, and when X is selected from O or S, no connection relationship exists between X and R 1; y is selected from halogen, unsubstituted or substituted alkoxy, unsubstituted or substituted phenol, substituted amino, unsubstituted or substituted straight chain alkyl; "substituted" means that at least one H in the substituted group is replaced by trimethylsilyl; representing a domain-separated key; and represents a coordination bond. The organometallic catalyst can realize the efficient ring-opening polymerization of the dioxanone under the condition of not adding an alcohol initiator to obtain the polydioxanone with the weight average molecular weight of 80 ten thousand; and the preparation method is nontoxic, good in biocompatibility and environment-friendly.

Description

Organometallic catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic catalysts, in particular to an organic metal catalyst, a preparation method and application thereof.
Background
Polydioxanone (PPDO) is an aliphatic polyester ether whose structural ester linkages impart excellent biodegradability, biocompatibility and bioresorbability to the polymer. In addition, the unique ether linkages in the molecular chain in turn give the polymer excellent toughness. These characteristics make PPDO successfully applied to the fields of high added value products such as surgical suture lines, orthopedic fixing materials, tissue repair materials, cell scaffolds, drug carriers and the like.
PPDO is obtained by ring-opening polymerization of a monomer to dioxanone, and to obtain PPDO with high molecular weight, the method can be realized by two ways, namely a one-step synthesis method of direct ring-opening polymerization and a two-step synthesis method of pre-polymerization and chain extension. The most reported method is a one-step method using PDO of high purity by ring-opening polymerization under the action of a high-efficiency catalyst. Obviously, the choice of catalyst is critical for the ring-opening polymerization of PDO. The catalysts commonly used mainly relate to the following classes: organotin, organozinc, organoaluminum, organorare earth, enzymatic catalysis, and the like. With the existing PPDO polymerization process, the high molecular weight PPDO is ensured, and the safety of the catalyst in the medical field is ensured, wherein the best-effect and most-used catalyst is stannous octoate, because the catalyst is one of the few catalysts approved by the United states food and drug administration to be used as a food additive. For example, patent (US patent 5652331) adopts stannous octoate and dodecanol as initiator to realize efficient ring-opening polymerization of PDO, and the molecular weight of PPDO is 81000 and the monomer conversion rate is 67%. The literature (polym. Bull.,2006,57,873) uses stannous octoate as a catalyst, and simultaneously adopts a microwave heating mode to carry out ring-opening polymerization, so that PPDO with high molecular weight can be obtained, and the polymerization time can be greatly shortened. Such as CN 112225886A, CN 113698586A, which adopts stannous octoate to catalyze PDO ring opening polymerization. Stannous octoate can efficiently catalyze PDO ring-opening polymerization reaction to prepare a high molecular weight colorless polymer, and the catalytic activity can be well maintained even when the catalyst is low in feeding. However, even so, the high toxicity of stannous octoate is the biggest obstacle to its use.
Therefore, development of a low-toxicity metal catalyst to realize efficient ring-opening polymerization of PDO has important scientific significance and application value. In order to solve the problem, several new catalysts are developed in the prior art, for example, in the journal document Raquez J M,Philippe Degée,Narayan R,et al."Coordination-insertion"ring-opening polymerization of 1,4-dioxan-2-one and controlled synthesis ofdiblock copolymers withε-caprolactone.Macromolecular Rapid Communications,2015,21(15),1063-1071., the patent discloses that the ring-opening polymerization of PDO is realized by adopting aluminum triisopropoxide (Al (OiPr) 3) as a catalyst, although the intrinsic viscosity of PPDO increases with the increase of the ratio of monomer to Al (OiPr) 3, and the reaction has certain controllability; however, the maximum intrinsic viscosity of the PPDO polymer synthesized is only 0.77dL/g and the conversion is only 70%.
U.S. Pat. No. 3, 4052988A (Doddi N, VERSFELT C C, wasselman D.synthetic absorbable surgical devices ofpoly-dioxanone) discloses the use of diethyl zinc (ZnEt 2) to catalyze the ring opening polymerization of PDO. However, the polymerization conditions in this document are severe, the polymerization time is long (72 hours), the molecular weight of the polymer is also low (intrinsic viscosity=0.70 dL/g), and ZnEt 2 has pyrophoricity, and is inconvenient to store and use.
Journal literature Kricheldorf H R,Damrau D O.Polylactones,42.Zn L-lactate-catalyzed polymerizations of 1,4-dioxan-2-one.Macromolecular Chemistry and Physics,1998,199,1089-1097. discloses that ring-opening polymerization of PDO is achieved using zinc lactate (ZnLac 2) which is convenient to synthesize and store. Although the viscosity of the polymer at 100℃for 14 days can reach 0.95dL/g when the ratio of monomer to catalyst is 2000:1, the monomer conversion is only 62%.
In addition, in the conventional organometallic catalysts, alcohol initiators are often used for ring-opening polymerization of dioxanone.
Disclosure of Invention
The invention aims to solve the problems that an alcohol initiator needs to be added when an organic metal catalyst for preparing polydioxanone is used in the prior art, the monomer conversion rate is low, the molecular weight of the prepared catalyst PPDO is low, or PPDO prepared by the toxicity of the catalyst cannot be used as a medical material, and the like, thereby providing an organic metal catalyst, a preparation method thereof and application thereof in lactone polymerization, in particular PDO ring-opening polymerization. The organometallic catalyst can realize the efficient ring-opening polymerization of the dioxanone under the condition of not adding an alcohol initiator, the monomer conversion rate is more than 85 percent, and the weight average molecular weight of the obtained polydioxanone is more than 48 ten thousand; meanwhile, the metal zinc, magnesium and iron in the organic metal catalyst adopted by the invention are nontoxic, cheap and easy to obtain, and are used as microelements of human bodies, so that the biological compatibility is good, the production process is more environment-friendly, and the prepared polydioxanone can be applied to the field of medical polymer materials.
In order to achieve the above purpose, the present invention provides the following technical solutions:
An organometallic catalyst having the structure of formula i:
wherein M is a divalent central metal ion;
R 1 is a C1-C10 straight or branched alkyl group; r 2 is C1-C6 straight or branched alkyl, n=0, 1, 2 or 3;
X is selected from N, O, S, P, when X is selected from N or P, X and R 1 are connected through a covalent bond, and when X is selected from O or S, no connection relationship exists between X and R 1;
Y is an initiating group selected from halogen, unsubstituted or substituted C1-C6 alkoxy, unsubstituted or substituted C6-C10 phenolic, substituted amino, unsubstituted or substituted C1-C10 linear or branched alkyl;
Wherein "substituted" in substituted C1-C6 alkoxy means that at least one H in the C1-C6 alkoxy is substituted with a C1-C5 straight or branched alkyl, trimethylsilyl;
"substituted" in a substituted C6-C10 phenolic group means that at least one H in the C6-C10 phenolic group is substituted with a C1-C5 alkyl, halogen, C1-C5 alkoxy, amino or trimethylsilyl group;
"substituted" in a substituted amino group means that at least one H in the amino group is substituted with a C1-C5 straight or branched chain alkyl, a C6-C10 aryl, or a trimethylsilyl group;
"substituted" of the substituted C1-C10 linear or branched alkyl groups is that at least one H of the substituted C1-C10 linear or branched alkyl groups is substituted with halogen, C6-C10 aryl or trimethylsilyl;
Representing a domain-separated key;
-represents a coordination bond;
-represents a single bond or is absent.
Alternatively, in the organometallic catalysts provided by the invention, R 1、R2 is independently selected from C1-C5 straight or branched alkyl groups;
r 1 is preferably methyl, ethyl, n-propyl, n-butyl, tert-butyl or n-pentyl; more preferably methyl, ethyl or n-butyl;
R 2 is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, isopentyl or t-pentyl; more preferably ethyl or tert-butyl;
n=0 or 2.
Optionally, in the organometallic catalyst provided by the invention, M is selected from any one of zinc ion (Zn 2+), magnesium ion (Mg 2+), iron ion (Fe 2+), cobalt ion (Co 2+) or nickel ion (Ni 2+); zinc ions (Zn 2+), iron ions (Fe 2+) or magnesium ions (Mg 2+) are preferred.
Optionally, in the organometallic catalyst provided by the invention, X is selected from N or O;
Y is selected from halogen, substituted amino or substituted C1-C3 straight chain alkyl, preferably any one of chloride, bromide, trimethylsilylmethyl, di (trimethylsilyl) methylene, tri (trimethylsilyl) methine, N- (trimethylsilyl) amino and N, N-di (trimethylsilyl) amino.
Optionally, in the organometallic catalyst provided by the invention, the organometallic catalyst has a structure shown in the following formula II or the following formula III:
The invention also provides a preparation method of the organometallic catalyst, which comprises the following steps:
the intermediate is obtained by reacting a compound of formula IV with a halide of M in an organic solvent,
Reacting the intermediate with a compound ZY to obtain an organometallic catalyst shown in a formula I;
M, X, n, Y, R 1 and R 2 are defined as above and are not described in detail;
Z is selected from any one of Li +、Na+ or K +, preferably Li + or K +.
Alternatively, in the preparation method of the organometallic catalyst provided by the invention, the organic solvent is conventional in the industry, so long as the compound of the formula IV can be dissolved, such as n-hexane, toluene, benzene, diethyl ether, ethylene glycol dimethyl ether or tetrahydrofuran. The reaction temperature and time of the specific IV compound and the halide of M can be regulated according to the activity of the actual reaction substrate, the reaction temperature recommended by the invention is 0-80 ℃ and the time is 0.1-12 hours, for example, the reaction temperature can be selected from 0 ℃,10 ℃, 30 ℃, 50 ℃, 80 ℃ and the like, and the reaction time can be selected from 1h, 2h, 4h, 6h, 8h, 10h, 12h and the like.
Optionally, in the preparation method of the organometallic catalyst provided by the invention, parameters of the reaction of the halide and the compound ZY are not particularly limited, and can be adjusted according to practical situations, for example, the reaction can be carried out for 0.1 to 12 hours at the temperature of-40 to 50 ℃. If the reaction temperature is selected from-40 ℃, -30 ℃, -10 ℃, 30 ℃, 50 ℃ and the like, the reaction time is selected from 1h, 2h, 4h, 6h, 8h, 10h, 12h and the like.
Optionally, in the preparation method of the organometallic catalyst provided by the invention, the compound shown in the formula IV can be prepared by adopting any existing preparation method, and structural identification is carried out.
Optionally, in the preparation method of the organometallic catalyst provided by the invention, the molar ratio of the compound shown in the formula IV to the halide of M to the compound ZY is 1: (0.2-1): (0.5-2); preferably 1: (0.5-1): (1.5-2), more preferably 1:1:2.
Optionally, in the preparation method of the organometallic catalyst provided by the invention, the halide of M is selected from MCl 2、MBr2、MI2, such as ferrous chloride, ferrous bromide, ferrous iodide, magnesium chloride, magnesium bromide, magnesium iodide, zinc chloride, zinc bromide or zinc iodide, etc.
Optionally, in the preparation method of the organic metal catalyst provided by the invention, the halide is directly reacted with the compound ZY without purification, after the reaction is finished, the post-treatment modes such as recrystallization and column chromatography are conventional in the industry, the recommended post-treatment modes are that the solvent in the reaction liquid after the reaction of the halide and the compound ZY is directly removed, and then the obtained solid is washed by using the solvent (the organic solvent which is slightly soluble, very slightly soluble, almost insoluble or insoluble in the organic rare earth catalyst, such as n-hexane, n-heptane and the like), so as to obtain the organic metal catalyst shown in the formula I.
The invention also provides the application of the organometallic catalyst or the organometallic catalyst prepared by the preparation method of the organometallic catalyst in the catalysis preparation of polyester materials; preferably in the catalytic preparation of polydioxanone.
The poly-p-dioxanone can be prepared by adopting the organometallic catalyst provided by the invention according to a conventional method for ring-opening polymerization of the p-dioxanone. The preparation method of the polydioxanone recommended by the invention comprises the following steps:
In an inert gas atmosphere, carrying out ring-opening polymerization on the dioxanone under the action of an organic metal catalyst to obtain poly-p-dioxanone;
wherein the organometallic catalyst is the organometallic catalyst described above or the organometallic catalyst prepared by the preparation method of the organometallic catalyst described above.
Alternatively, in the method for preparing polydioxanone proposed by the present invention, inert gas may be selected from those conventionally used in the art, such as nitrogen, argon, helium, etc.
Optionally, in the preparation method of the polydioxanone recommended by the invention, the reaction parameters are not particularly limited, and the reaction time recommended by the invention is 60-120 ℃ and 1-6 h; specifically, the catalyst is adjusted according to the catalytic activity and the addition amount of the actual organometallic catalyst, such as 110 ℃,100 ℃, 90 ℃, 80 ℃, 70 ℃, 60 ℃,1h, 2h, 3h, 4h, 5h and 6h.
In the preparation method of the polydioxanone, preferably, in the atmosphere of inert gases (such as nitrogen, argon, helium and the like), the polydioxanone monomer and the organic solvent are added into a reaction device, and after the temperature is raised and the reaction temperature is maintained stable, the organometallic catalyst is added for reaction.
After the reaction for preparing the polydioxanone is finished, the method can be carried out according to a post-treatment mode conventional in the industry, such as recrystallization, and the like, and the post-treatment mode recommended by the invention is as follows: after the reaction is finished, the polymerization is stopped firstly (ice bath, ice salt bath or other modes can be adopted), then a solvent which can dissolve the product, such as 1, 2-tetrachloroethane, is used for dissolving the product PPDO, then methanol or ethanol is added for precipitating the product PPDO, and the separated precipitate is dried to obtain PPDO, so that the post-treatment mode is convenient and quick, and the yield is high.
Optionally, in the preparation method of the polydioxanone provided by the invention, the molar ratio of the organometallic catalyst to the polydioxanone is 1:5000-16000. The specific amount of the organometallic catalyst can be adjusted according to the molecular weight requirement of the actual polydioxanone, the catalytic activity of the catalyst and the like, such as 1:5000, 1:7000, 1:9000, 1:13000, 1:15000 and the like.
Compared with the prior art, the invention has the following beneficial effects:
1. The organometallic catalyst provided by the invention can realize the efficient ring-opening polymerization of the dioxanone without adding an alcohol initiator when being used for ring-opening polymerization of the dioxanone, and the weight average molecular weight of the prepared polydioxanone reaches 80 ten thousand. Meanwhile, the metal zinc, magnesium and iron in the organic metal catalyst provided by the invention are nontoxic, cheap and easy to obtain, and are used as trace elements necessary for human bodies, the biocompatibility is good, the production process is more environment-friendly, and the polydioxanone prepared by catalysis of the organic catalyst can be applied to the field of medical polymer materials.
2. The organometallic catalyst provided by the invention can realize the efficient controllable ring-opening polymerization of PDO monomer, the polymerization reaction has the advantages of high activity, easy regulation, mild reaction and the like, the monomer conversion rate is more than 85%, and the obtained PPDO polymer has the advantages of large molecular weight and narrow molecular weight distribution (the weight average molecular weight is 20 ten thousand-80 ten thousand, and the molecular weight distribution is 1.05-1.20).
Detailed Description
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of illustration and are not to be construed as limiting the scope of the invention, as many insubstantial modifications and variations of the invention will become apparent to those skilled in the art in light of the above disclosure.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
The technical scheme of the present invention is further described by the following specific examples, which should not be construed as limiting the invention.
The above-mentioned compounds 2 and 3 were prepared according to the methods in the following corresponding documents, respectively, and confirmed by HPLC-MS, 1HNMR、13 CNMR, the specific corresponding documents being as follows:
Compound 2
Wang,W.,Inoue,S.,Irran,E.,Driess,M.(2012).Synthesis and Unexpected Coordination of a Silicon(II)-Based SiCSi Pincerlike Arene to Palladium.Angewandte Chemie International Edition,51(15),3691-3694.
Compound 3
Gallego,D.,Inoue,S.,Blom,B.,Driess,M.(2014).Highly electron-rich pincer-type iron complexes bearing innocent bis(metallylene)pyridine ligands:syntheses,structures,and catalytic activity.Organometallics,33(23),6885-6897.
Example 1
Preparation of organometallic catalyst 1
The silylene ligand 2 (7.40 g, fw= 740.2, 10 mmol) and ZnCl 2 (1.36 g, fw=136.3, 10 mmol) were added to a schlenk flask, 30mL of tetrahydrofuran was introduced at 0 ℃ and reacted for 2 hours at 0 ℃ to give silylene ligand-stabilized dihalide, then 20mL of a 1m KN (SiMe 3)2 (3.99 g, fw=199.48, 20 mmol) tetrahydrofuran solution was slowly dropped into the above solution (about 30 minutes) at 0 ℃, the system was slowly warmed to room temperature and stirred for 12 hours, after the solvent was pumped down, 10mL of pentane was added and washed, the white powder organometallic catalyst 1 (10.14 g, yield 90%, fw= 1126.35) was obtained.
The structure was characterized by 1 H NMR, elemental analysis and melting point.
The melting point of the organometallic catalyst 1 is 248-250 ℃.
Elemental analysis data for C55H101N7O2Si6 Zn: calculated values: c,58.65; h,9.04; n,8.71. Found: c,58.59; h,9.07; n,8.67.
Nuclear magnetic data ：1H NMR(500MHz,CDCl3)δ7.58(s,1H),7.47-7.42(m,2H),7.40-7.35(m,4H),7.27-7.22(m,4H),1.45(s,18H),1.25(d,J＝13.6Hz,36H),0.28(s,36H).
Examples 2 to 3
Examples 2 to 3 provide similar preparation methods to example 1, except that the raw material metal dihalides used were different, and the compounds magnesium chloride and ferrous bromide were used in examples 2 to 3 instead of zinc chloride in example 1, respectively, and the structures of the organometallic catalysts 2 to 3 obtained in examples 2 to 3 were as follows:
The organometallic catalyst 2 was a white solid. Yield 92% (fw= 1085.28), melting point 254-256 ℃; elemental analysis (for C55H101MgN7O2Si 6): calculated values: c,60.87; h,9.38; n,9.03. Found: c,60.89; h,9.41; n,9.05.
Nuclear magnetic data ：1H NMR(500MHz,CDCl3)δ7.55(s,1H),7.41-7.36(m,2H),7.29-7.23(m,4H),7.22-7.17(m,4H),1.36(s,18H),1.12(d,J＝13.6Hz,36H),0.23(s,36H).
The organometallic catalyst 3 is a white solid. Yield 94% (fw= 1116.82), melting point 255-257 ℃; elemental analysis (for C55H101FeN7O2Si 6): calculated values: c,59.15; h,9.12; n,8.78. Found: c,59.11; h,9.07; n,8.72.
Nuclear magnetic data ：1H NMR(500MHz,CDCl3)δ7.49(s,1H),7.34-7.33(m,2H),7.31-7.25(m,4H),7.18-7.12(m,4H),1.35(s,18H),1.19(d,J＝13.6Hz,36H),0.24(s,36H).
Example 4
The silylene ligand 3 (6.82 g, fw= 682.12, 10 mmol) and ZnCl 2 (1.36 g, fw=136.3, 10 mmol) were added to a schlenk flask, 30mL of tetrahydrofuran was introduced at 30 ℃ and reacted at 30 ℃ for 3 hours to give silylene ligand-stabilized dihalide, and then 20mL of 1m LiCH 2SiMe3 (1.88 g, fw=94.16, 20 mmol) in n-hexane was added dropwise to the above solution (about 30 minutes) and reacted at 50 ℃ for 6 hours. After the solvent was drained, 10mL of n-hexane was added to wash, and then, a white powdery organometallic catalyst 4 (8.48 g, yield 92%, fw= 921.93) was obtained.
The melting point of the organometallic catalyst 4 is 272-274 ℃.
Elemental analysis data for C47H81N7Si4 Zn: calculated values: c,61.23; h,8.86; n,10.64. Found: c,61.19; h,8.82; n,10.62.
Nuclear magnetic data ：1H NMR(500MHz,CDCl3)δ7.48-7.42(m,2H),7.41-7.35(m,4H),7.28-7.21(m,4H),7.02(d,J＝7.5Hz,1H),6.75(d,J＝7.5Hz,2H),3.65(q,J＝8.0Hz,4H),2.01(s,4H),1.24(d,J＝29.9Hz,42H),-0.07(s,18H).
Examples 5 to 6
Examples 5 to 6 provide similar preparation methods to example 4, except that the raw material metal dihalides used were different, and the compounds magnesium chloride and ferrous bromide were used in examples 5 to 6 instead of zinc chloride in example 1, respectively, and the structures of the organometallic catalysts 5 to 6 prepared in examples 2 to 3 were as follows:
The organometallic catalyst 5 is a white solid. Yield 94% (fw= 880.86), melting point 276-278 ℃; elemental analysis (for C47H81N7Si4 Mg): calculated values: c,64.09; h,9.27; n,11.13. Found: c,64.13; h,9.32; n,11.15.
Nuclear magnetic data ：1H NMR(500MHz,CDCl3)δ7.45-7.39(m,2H),7.37-7.31(m,4H),7.18-7.11(m,4H),6.92(d,J＝7.5Hz,1H),6.62(d,J＝7.5Hz,2H),3.61(q,J＝8.0Hz,4H),1.98(s,4H),1.22(d,J＝29.9Hz,42H),-0.08(s,18H).
The organometallic catalyst 6 is a red solid. Yield 95% (fw= 912.40), melting point 280-282 ℃; elemental analysis (for C47H81N7Si4 Fe): calculated values: c,61.87; h,8.95; n,10.75. Found: c,61.84; h,8.91; n,10.69.
Nuclear magnetic data ：1H NMR(500MHz,CDCl3)δ7.37-7.32(m,2H),7.33-7.24(m,4H),7.19-7.11(m,4H),6.90(d,J＝7.5Hz,1H),6.65(d,J＝7.5Hz,2H),3.61(q,J＝8.0Hz,4H),2.08(s,4H),1.18(d,J＝29.9Hz,42H),-0.06(s,18H).
Example 7
The organic rare earth catalyst 1 prepared in the example 1 is used for catalyzing the paradioxanone to prepare the polydioxanone, and the reaction formula is shown as follows:
The procedure was carried out in a glove box in an anhydrous and anaerobic environment, PDO monomer (20.4 g, fw=102.1, 200 mmol) and 40mL toluene were added to a polymerization flask having an effective volume of 100mL, and the polymerization flask containing the monomer was placed in a constant temperature oil bath at 60 ℃. After constant temperature, a toluene solution (22.5 mg,0.02 mmol) of the organometallic catalyst 1 was further added, and polymerization was carried out for 6 hours. The polymerization bottle was taken out of the glove box, put into ice bath to terminate polymerization, cooled to room temperature, and 50mL of a mixed solvent of 1, 2-tetrachloroethane and phenol (volume ratio 1:1) was added to dissolve the product, then methanol was added to precipitate the polymer, and the precipitated polymer was dried in vacuo and weighed, and the specific results are shown in Table 1.
Example 8
The procedure was carried out in a glove box in an anhydrous and anaerobic environment, PDO monomer (20.4 g, fw=102.1, 200 mmol) and 40mL toluene were added to a polymerization flask having an effective volume of 100mL, and the polymerization flask containing the monomer was placed in a constant temperature oil bath at 110 ℃. After the temperature had been kept constant, a toluene solution (14.5 mg,0.013 mmol) of the organometallic catalyst 2 was further added and the polymerization was continued for 3 hours. The polymerization bottle was taken out of the glove box, put into ice bath to terminate polymerization, cooled to room temperature, and 50mL of a mixed solvent of 1, 2-tetrachloroethane and phenol (volume ratio 1:1) was added to dissolve the product, then methanol was added to precipitate the polymer, and the precipitated polymer was dried in vacuo and weighed, and the specific results are shown in Table 1.
Example 9
The procedure was carried out in a glove box in an anhydrous and anaerobic environment, PDO monomer (20.4 g, fw=102.1, 200 mmol) and 40mL toluene were added to a polymerization flask with an effective volume of 100mL, and the polymerization flask with the monomer was placed in a constant temperature oil bath at 70 ℃. After the temperature had been kept constant, a toluene solution (27.9 mg,0.025 mmol) of the organometallic catalyst 3 was added thereto and the mixture was polymerized for 4 hours. The polymerization bottle was taken out of the glove box, put into ice bath to terminate polymerization, cooled to room temperature, and 50mL of a mixed solvent of 1, 2-tetrachloroethane and phenol (volume ratio 1:1) was added to dissolve the product, then methanol was added to precipitate the polymer, and the precipitated polymer was dried in vacuo and weighed, and the specific results are shown in Table 1.
Example 10
The procedure was carried out in a glove box in an anhydrous and anaerobic environment, PDO monomer (20.4 g, fw=102.1, 200 mmol) and 40mL toluene were added to a polymerization flask having an effective volume of 50mL, and the polymerization flask containing the monomer was placed in a constant temperature oil bath at 70 ℃. After a certain period of constant temperature, a toluene solution (18.4 mg,0.02 mmol) of the organometallic catalyst 4 was added thereto and polymerized for 5 hours. The polymerization bottle was taken out of the glove box, put into ice bath to terminate polymerization, cooled to room temperature, and 50mL of a mixed solvent of 1, 2-tetrachloroethane and phenol (volume ratio 1:1) was added to dissolve the product, then methanol was added to precipitate the polymer, and the precipitated polymer was dried in vacuo and weighed, and the specific results are shown in Table 1.
Example 11
The procedure was carried out in a glove box in an anhydrous and anaerobic environment, PDO monomer (20.4 g, fw=102.1, 200 mmol) and 40mL toluene were added to a polymerization flask having an effective volume of 50mL, and the polymerization flask containing the monomer was placed in a constant temperature oil bath at 80 ℃. After the temperature had been kept constant, a toluene solution (11.7 mg,0.013 mmol) of the organometallic catalyst 5 was further added, and the polymerization was continued for 3 hours. The polymerization bottle was taken out of the glove box, put into ice bath to terminate polymerization, cooled to room temperature, and 50mL of a mixed solvent of 1, 2-tetrachloroethane and phenol (volume ratio 1:1) was added to dissolve the product, then methanol was added to precipitate the polymer, and the precipitated polymer was dried in vacuo and weighed, and the specific results are shown in Table 1.
Example 12
The procedure was carried out in a glove box in an anhydrous and anaerobic environment, PDO monomer (20.4 g, fw=102.1, 200 mmol) and 40mL toluene were added to a polymerization flask having an effective volume of 50mL, and the polymerization flask containing the monomer was placed in a constant temperature oil bath at 120 ℃. After the temperature was kept constant, a toluene solution (20.3 mg,0.022 mmol) of the organometallic catalyst 6 was further added, and after polymerization for 1 hour. The polymerization bottle was taken out of the glove box, put into ice bath to terminate polymerization, cooled to room temperature, and 50mL of a mixed solvent of 1, 2-tetrachloroethane and phenol (volume ratio 1:1) was added to dissolve the product, then methanol was added to precipitate the polymer, and the precipitated polymer was dried in vacuo and weighed, and the specific results are shown in Table 1.
Comparative example 1
The method of preparation PPDO provided in this comparative example is similar to that of example 9, except that the catalyst used is different in structure from that used in this comparative example as shown in formula V below. The catalyst is prepared according to the literature C mpora, j., naz, a.m., palma, p.,E.,&Reyes,M.L.(2005).2,6-Diiminopyridine iron(II)dialkyl complexes.Interaction with aluminum alkyls and ethylene polymerization catalysis.Organometallics,24(21),4878-4881 The catalyst prepared by the method is structurally confirmed by nuclear magnetism, mass spectrum and melting point.
Comparative example 2
The procedure for preparation PPDO provided in this comparative example is similar to that of example 12, except that the catalyst used is different and the catalyst structure used in this comparative example is shown in formula VI. The catalyst is prepared according to the method in literature Liu,J.,Yang,G.,Liu,Y.,Zhang,D.,Hu,X.,&Zhang,Z.(2020).Efficient conversion ofCO2 into cyclic carbonates at room temperature catalyzed by Al-salen andimidazolium hydrogen carbonate ionic liquids.Green Chemistry,22(14),4509-4515, the prepared ligand is subjected to structure confirmation through nuclear magnetism and mass spectrum, and the prepared catalyst is subjected to structure confirmation through nuclear magnetism, mass spectrum and melting point.
Table 1 shows the results of the polymerization test
aMw : Weight average molecular weight, as measured by gel permeation chromatography; b PDI: molecular weight distribution, as measured by gel permeation chromatography.
As can be seen from the data in the table, when the organometallic catalyst provided by the invention is used for catalyzing PDO ring-opening polymerization to prepare PPDO, the catalyst has high catalytic activity without adding alcohol initiator, the monomer conversion rate is more than 85%, the weight average molecular weight of the obtained polydioxanone is more than 48 ten thousand, and the molecular weight distribution is narrower. The catalysts used in comparative examples 1 and 2 were not only low in activity, but also low in molecular weight of PPDO obtained.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (10)

1. An organometallic catalyst characterized by having the structure of formula i:
Wherein M is a divalent metal ion;
R 1 is a C1-C10 straight or branched alkyl group; r 2 is C1-C6 straight or branched alkyl, n=0, 1, 2 or 3;
X is selected from N, O, S, P, when X is selected from N or P, X and R 1 are connected through a covalent bond, and when X is selected from O or S, no connection relationship exists between X and R 1;
Y is an initiating group selected from halogen, unsubstituted or substituted C1-C6 alkoxy, unsubstituted or substituted C6-C10 phenolic, substituted amino, unsubstituted or substituted C1-C10 linear or branched alkyl;
Representing a domain-separated key;
And represents a coordination bond.
2. The organometallic catalyst according to claim 1, wherein each R 1、R2 is independently selected from C1-C5 linear or branched alkyl;
r 1 is preferably methyl, ethyl, n-propyl, n-butyl, tert-butyl or n-pentyl; more preferably methyl, ethyl or n-butyl;
R 2 is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, isopentyl or t-pentyl; more preferably ethyl or tert-butyl;
n=0 or 2.
3. The organometallic catalyst according to claim 1, wherein M is selected from any of zinc ion (Zn 2+), magnesium ion (Mg 2 +), iron ion (Fe 2+), cobalt ion (Co 2+) or nickel ion (Ni 2+); zinc ion, iron ion or magnesium ion is preferable.
4. The organometallic catalyst according to claim 1, wherein X is selected from N or O;
Y is selected from halogen, substituted amino or substituted C1-C3 straight chain alkyl, preferably any one of chloride, bromide, trimethylsilylmethyl, di (trimethylsilyl) methylene, tri (trimethylsilyl) methine, N- (trimethylsilyl) amino and N, N-di (trimethylsilyl) amino.
5. The organometallic catalyst according to claim 1, wherein the organometallic catalyst has a structure represented by the following formula II or the following formula III:
6. A method for preparing an organometallic catalyst, comprising the steps of:
Reacting a compound of formula IV with a halide of M to obtain an intermediate;
reacting the intermediate with a compound ZY to obtain an organometallic catalyst shown in a formula I;
M, X, n, Y, R 1 and R 2 are as defined in any one of claims 1 to 5;
Z is selected from any one of Li +、Na+ or K +, preferably Li + or K +.
7. The process according to claim 6, wherein the molar ratio of the compound of formula IV, the halide of the metal ion M and the compound ZY is 1: (0.2-1): (0.5-2); preferably 1: (0.5-1): (1.5-2).
8. Use of an organometallic catalyst according to any one of claims 1 to 5 or prepared by the method for preparing an organometallic catalyst according to claim 6 or 7 for the catalytic preparation of a polyester material; preferably in the catalytic preparation of polydioxanone.
9. A method for preparing polydioxanone, which is characterized by comprising the following steps:
In an inert gas atmosphere, carrying out ring-opening polymerization on the dioxanone under the action of an organic metal catalyst to obtain poly-p-dioxanone;
Wherein the organometallic catalyst is the organometallic catalyst according to any one of claims 1 to 5 or the organometallic catalyst produced by the method for producing an organometallic catalyst according to claim 6 or 7.
10. The process for preparing polydioxanone according to claim 9, wherein the molar ratio of the organometallic catalyst to the polydioxanone is from 1:5000 to 16000.
CN202211598856.4A 2022-12-12 2022-12-12 Organometallic catalyst and preparation method and application thereof Pending CN118184981A (en)

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