CN107417900B - Zinc coordination polymer catalyst for preparing polyglycolic acid and preparation method thereof - Google Patents
Zinc coordination polymer catalyst for preparing polyglycolic acid and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a zinc coordination polymer catalyst for preparing polyglycolic acid and a preparation method thereof, and relates to the field of polyglycolic acid catalysts. The chemical formula is [ Zn (BDC) L ], wherein BDC is terephthalate anion, and L is 2,3,5, 6-tetrachloro-N, N' -di (4-pyridine) diamide ligand. The invention adopts zinc nitrate hexahydrate, organic ligand terephthalic acid and 2,3,5, 6-tetrachloro-N, N' -di (4-pyridine) diamide to prepare the zinc coordination polymer containing the quadruple interpenetrating diamond three-dimensional network structure in N, N-dimethylformamide through thermal reaction under a closed condition. The synthesis method disclosed by the invention has high yield and good reproducibility; the obtained crystal has high purity. The zinc coordination polymer has good catalytic activity for catalyzing the ring-opening polymerization of glycolide, and the prepared polyglycolic acid has the weight-average molecular weight of more than 6 ten thousand, and can be applied to the field of medical high polymer materials.
Description
Technical Field
The invention relates to the field of polyglycolic acid catalysts, and in particular relates to a zinc coordination polymer, a preparation method thereof and application thereof in catalyzing ring-opening polymerization of glycolide bodies.
Background
Polyglycolic acid, also known as polyglycolic acid, abbreviated as PGA, is a linear aliphatic polyester with the simplest structure, and is the first synthetic polymer material approved by the FDA in the United states for use as absorbable surgical suture (trade name Dexon)@). Because PGA has the characteristics of good biocompatibility, no toxicity, adjustable degradation and the like, the PGA has wide application prospect in the aspects of medical absorbable surgical suture, drug slow release/controlled release carrier materials, simulated human tissue materials, biodegradable polymer scaffold materials and the like (Middleton J.C., Tipton A.J.biomaterials 2000,21, 2335-2346).
PGA can be synthesized mainly by a direct polycondensation method and a ring-opening polymerization method. The direct polycondensation method is to directly dehydrate and polycondense glycolic acid, but the molecular weight distribution of the PGA synthesized by the method is too wide, the molecular weight is low and is not easy to control, and the mechanical property is poor. The ring-opening polymerization method is divided into solution ring-opening polymerization and bulk ring-opening polymerization, and the solution ring-opening polymerization refers to the ring-opening polymerization of glycolide in an organic solution promoted by a metal complex, an organic compound or an enzyme catalyst, which is a common method for synthesizing high-molecular-weight PGA. However, since a large amount of high boiling point solvent is used in the ring-opening polymerization process of the solution, the post-treatment process is complicated and causes environmental pollution, the production cost is increased, and the large-scale commercial production is not facilitated. Compared with the solution ring-opening polymerization method, the bulk ring-opening polymerization method does not use any solvent, reduces post-treatment processes and greatly reduces the production cost.
Bulk ring-opening polymerization of glycolide requires initiation of a catalyst, otherwise the relative molecular mass is difficult to improve. At present, stannous octoate and stannous chloride are considered to be catalysts which are widely applied and have higher efficiency in catalyzing the ring-opening polymerization of glycolide bodies to prepare high-molecular-weight PGA. However, tin compounds have certain cytotoxicity and wide molecular weight distribution in the process of catalyzing the ring-opening polymerization of glycolide, which is not favorable for the application of polyglycolic acid in the field of medical polymer materials. Researches show that main group metals such as aluminum, calcium, magnesium and bismuth, transition metals such as zinc, titanium and zirconium and lanthanide complexes also have the performance of catalyzing ring-opening polymerization of lactones (Dechy-Cabaret O., Martin-Vaca B., Bourissou D.Chem.Rev.2004,104, 6147-6176; Labet M, Thielemans W.Chem.Soc.Rev.2009,38, 3484-. Therefore, research and development of new metal complexes for synthesizing PGA with low toxicity, high molecular weight and narrow molecular weight distribution has wide application prospect, and strong vitality is also injected for research and injection of biomedical degradable high polymer materials.
Disclosure of Invention
The invention aims to further develop the application of a zinc complex in catalyzing the ring-opening polymerization of glycolide to prepare PGA, and discloses a zinc coordination polymer catalyst, a preparation method thereof and application of the zinc coordination polymer catalyst in catalyzing the ring-opening polymerization of glycolide to prepare PGA. The synthesis method of the zinc coordination polymer catalyst has high yield and good reproducibility; the obtained crystal has high purity. The zinc coordination polymer has good catalytic activity for catalyzing the ring-opening polymerization of glycolide, and the prepared polyglycolic acid has the weight-average molecular weight of more than 6 ten thousand, and can be applied to the field of medical high polymer materials.
The invention relates to a zinc coordination polymer catalyst applied to catalyzing ring-opening polymerization of glycolide, which has a chemical formula of [ Zn (BDC) L ], wherein BDC is terephthalate anion, and L is a 2,3,5, 6-tetrachloro-N, N' -bis (4-pyridine) diamide ligand.
The invention relates to a zinc coordination polymer catalyst for catalyzing ring-opening polymerization of glycolide, which comprises the following secondary structure units: the crystal belongs to monoclinic system and has space group P21C, molecular formula is C26H12Cl4N4O6Zn, molecular weight 683.59; the unit cell parameters are:
α is 90 °, β is 120.722(7 °), γ is 90 °, unit cell volume is
The basic structure is a three-dimensional network structure containing quadruple interpenetration of diamond.
The preparation method of the zinc coordination polymer catalyst for catalyzing the ring opening polymerization of glycolide comprises the following steps: putting zinc nitrate hexahydrate, terephthalic acid, 2,3,5, 6-tetrachloro-N, N' -bis (4-pyridine) diamide and N, N-dimethylformamide into a reactor, sealing the reactor, and reacting at 100 ℃ for 24 hours; and after the reaction is finished, cooling to room temperature to obtain the zinc coordination polymer catalyst crystal, and then washing with N, N-dimethylformamide and ethanol in sequence and drying to obtain the zinc coordination polymer catalyst crystal.
In the technical scheme, zinc nitrate hexahydrate and terephthalic acid are mixed according to a molar ratio of 2,3,5, 6-tetrachloro-N, N' -bis (4-pyridine) diamide to 1:1: 1.
In the above technical scheme, every 0.1 mmol of terephthalic acid corresponds to 6ml of N, N-dimethylformamide.
In the above technical scheme, in the step, the cooling rate is 5 ℃/hour.
The method for preparing the polyglycolic acid by catalyzing the ring-opening polymerization of the glycolide by the zinc coordination polymer is characterized by comprising the following steps: adding the zinc coordination polymer catalyst and glycolide into a stainless steel sealed tube, heating to 210 ℃, and carrying out bulk ring-opening polymerization for 3 hours to obtain polyglycolic acid
Wherein the molar ratio of the zinc coordination polymer catalyst to the glycolide is 1: 4000; the weight average molecular weight of the obtained PGA is 64390, and the PGA can be applied to the field of medical polymer materials.
The invention has the advantages that: the synthetic method has convenient operation, high yield and good reproducibility. The zinc coordination polymer catalyst has excellent catalytic activity on the ring opening of glycolide, and the prepared PGA has the weight-average molecular weight of more than 6 ten thousand, and can be applied to the field of medical high polymer materials.
Drawings
Wherein FIG. 1 is a diagram showing a coordination environment of zinc ions in a zinc coordination polymer catalyst;
wherein FIG. 2 is a schematic diagram of a single diamond cage structure in a zinc coordination polymer catalyst;
wherein FIG. 3 is a schematic diagram of a quadruple interpenetrating three-dimensional diamond network structure in a zinc coordination polymer catalyst;
wherein FIG. 4 is a powder diffraction diagram of a zinc coordination polymer catalyst;
wherein FIG. 5 is a schematic diagram of the reaction rate and reaction time of glycolide ring-opening polymerization initiated by the zinc coordination polymer catalyst;
wherein, FIG. 6 is a schematic diagram of the conversion rate and reaction time of glycolide ring-opening polymerization initiated by the zinc coordination polymer catalyst.
Detailed Description
Experimental example 1 preparation of zinc coordination polymer catalyst:
29.7 mg of zinc nitrate hexahydrate (0.1 mmol), 16.6 mg of terephthalic acid (0.1 mmol), 29.6 mg of 2,3,5, 6-tetrachloro-N, N' -bis (4-pyridine) diamide (0.1 mmol) and 6ml of N, N-dimethylformamide were charged into a reactor, and the mixture was allowed to stand at 100 ℃ for 24 hours to obtain crystals, which were then washed with N, N-dimethylformamide and ethanol in this order and dried to obtain a zinc complex polymer catalyst with a yield of 65% (44.4 mg based on terephthalic acid).
The main infrared absorption peak is (KBr/cm)–1)：3411br,3249m,3170m,3072m,1712s,1662s,1637s,1602s,1532s,1435s,1410s,1248m,1221s,1173m,840s,770s,678m,448m。
Characterization of test-Zinc coordination Polymer catalyst
(1) Crystal structure determination of zinc coordination polymer catalyst
The crystal structure was determined using a Bruker Apex II CCD diffractometer at 293(2) K with Mo K α radiation monochromatized with graphite
Diffraction points were collected in an omega scan fashion, and the collected data were reduced by the SAINT program and corrected for semi-empirical absorption using the SADABS method. The structure analysis and refinement are respectively completed by SHELX and SHELX of SHELXTL program, and F is processed by full matrix least square method2And correcting to obtain the coordinates and anisotropic parameters of all non-hydrogen atoms. All hydrogen atoms are theoretically fixed on the parent atom during the structure refinement process, giving an isotropic displacement parameter slightly (C-H, 1.2 or N-H, 1.2 times) larger than the parent atom displacement parameter. The detailed crystal determination data are shown in table 1. The structure is shown in figures 1-3. FIG. 1: a coordination environment diagram of zinc ions in the zinc coordination polymer catalyst; FIG. 2: schematic diagram of single diamond cage structure in zinc coordination polymer catalyst; FIG. 3 is a schematic diagram of a quadruple interpenetrating three-dimensional diamond network structure in a zinc coordination polymer catalyst.
(2) Phase purity characterization of zinc coordination polymer catalysts
The powder diffraction characterization of the complex shows that the complex has reliable phase purity, and provides guarantee for the application of the complex as a catalyst for the ring-opening polymerization of glycolide. See fig. 4. (Instrument model: Rigaku D/Max-2500)
Study on evaluation of glycolide ring-opening polymerization performance initiated by zinc coordination polymer catalyst by test two DSC method
10000mg of glycolide (86.0 mmol) and 14.7mg of zinc coordination polymer catalyst (0.02 mmol) are mixed in a pulverizer, 5mg of sample is placed in an aluminum crucible, DSC enthalpy change is measured, and the relationship between the reaction rate and the reaction time of the zinc coordination polymer catalyzed glycolide ring-opening polymerization and the relationship between the conversion rate and the reaction time of the glycolide are obtained by calculation, as shown in figures 5 and 6. FIG. 5: a schematic diagram of the reaction rate and the reaction time of the ring-opening polymerization of glycolide initiated by the zinc coordination polymer catalyst; FIG. 6: the zinc coordination polymer catalyst initiates the ring opening polymerization conversion rate and the reaction time of the glycolide.
Experiment shows that the tri-zinc coordination polymer catalyst initiates the ring-opening polymerization of glycolide body to prepare PGA
10000mg of glycolide (86.0 mmol) and 13.7mg of zinc coordination polymer catalyst (0.02 mmol) are added into a stainless steel sealed tube, the temperature is rapidly raised to 210 ℃, the reaction is carried out for 3 hours under the condition of heat preservation, and the white PGA product is obtained after cooling to the room temperature.
Testing the determination of the molecular weight of TetraPGA
10mg of PGA was dissolved in 5mL of a hexafluoroisopropanol solution having a sodium trifluoroacetate content of 5mmol/L, filtered through a 0.4 μm-pore polytetrafluoroethylene filter, and 20 μ L of the filtrate was introduced into a "LC-20 AD GPC" sample injector (manufactured by Shimadzu corporation), whereby the weight average molecular weight was 64390.
And (3) testing conditions are as follows: the column temperature is 40 ℃; eluent: hexafluoroisopropanol with 5mmol/L of sodium trifluoroacetate dissolved therein; the flow rate is 0.6 mL/min; a detector: an RI detector; and (3) correction: five different standards of polymethyl methacrylate with molecular weights varying from 2000 to 100000 were used for molecular weight correction.
TABLE 1 Primary crystallography data for Zinc coordination Polymer catalysts
Claims (2)
1. A preparation method of a zinc coordination polymer catalyst applied to catalyzing ring-opening polymerization of glycolide has a chemical formula of [ Zn (BDC) L ], wherein BDC is terephthalate anion, and L is 2,3,5, 6-tetrachloro-N, N' -bis (4-pyridine) diamide ligand;
the secondary structure unit is as follows: the crystal belongs to monoclinic system and has space group ofP21/cMolecular formula is C26H12Cl4N4O6Zn with molecular weight of 683.59, unit cell parameters of a = 15.529(2) Å, b = 18.617(2) Å, c = 19.3430(19) Å =90 °, β = 120.722(7) °, γ =90 °, unit cell volume of 4807.3(10) Å3；
The method is characterized by comprising the following steps: putting zinc nitrate hexahydrate, terephthalic acid, 2,3,5, 6-tetrachloro-N, N' -bis (4-pyridine) diamide and N, N-dimethylformamide into a reactor, sealing the reactor, and reacting at 100 ℃ for 24 hours; cooling to room temperature after the reaction is finished to obtain the zinc coordination polymer catalyst crystal, and then washing with N, N-dimethylformamide and ethanol in sequence and drying to obtain the zinc coordination polymer catalyst crystal;
zinc nitrate hexahydrate to terephthalic acid 2,3,5, 6-tetrachloro-N, N' -bis (4-pyridine) diamide =1: 1:1 in mole ratio;
6ml of N, N-dimethylformamide per 0.1 mmol of terephthalic acid;
in the step, the cooling rate is 5 ℃/hour.
2. The method for preparing polyglycolic acid by glycolide ring-opening polymerization catalyzed by zinc coordination polymer as claimed in claim 1, which is characterized by comprising the following steps: adding the zinc coordination polymer catalyst and glycolide into a stainless steel sealed tube, heating to 210 ℃, and carrying out a bulk ring-opening polymerization reaction for 3 hours to obtain polyglycolic acid;
the molar ratio of the zinc coordination polymer catalyst to glycolide is 1: 4000; the obtained polyglycolic acid has weight average molecular weight of 64390, and can be applied in the field of medical polymer materials.
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Non-Patent Citations (3)
| Title |
|---|
| Basic Catalytic Performance of Amino and Acylamide;SONG Lili,等;《Chem. Res. Chin. Univ.》;20161231;第32卷(第5期);838-842 * |
| Heterogeneous catalysis with coordination modulation synthesized MOF: Morphology-Dependent catalytic Activity;Massomeh Ghorbanloo等;《ROYAL SOCIETY OF CHEMISTRY》;20131231;1-9 * |
| Isomorphic MOFs functionalized by free-standing;Lili Song;《ROYAL SOCIETY OF CHEMISTRY》;20161231(第40期);2904-2909 * |
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