ORGANIC FRAME MATERIAL HAVING ISOPOLY-MOLYBDIC ACID METAL FOR MANUFACTURING POLYLACTIC ACID AND METHOD OF MANUFACTURING THE SAME

Abstract

An organic frame material having isopoly-molybdic acid metal for manufacturing polylactic acid and method of manufacturing the same is provided. The chemical formula of the organic frame material having isopoly-molybdic acid metal is [Cu(tfbtb).sub.0.5(β-Mo.sub.8O.sub.26)0.5(H.sub.2O)]. tfbtb is a 2,3,5,6-tetrafluoro-bis (1,2,4-triazole-1-methyl) benzene ligand, and [β-Mo.sub.8O.sub.26] is a β type octamolybdate anion. Sodium molybdate dihydrate, copper salt and organic ligand 2,3,5,6-tetrafluoro-bis (1,2,4-triazole-1-methyl) benzene undergo hydrothermal reaction in a closed condition to form the organic frame material having copper containing isopoly-molybdic acid metal that has a three-dimensional structure. The synthesis method is simple with high yield and reproducibility. The organic frame material having isopoly-molybdic acid metal shows high catalytic activity towards the ring-opening polymerization of lactide. The resulting polylactic acid has a weight average molecular weight exceeding 60,000. The polylactic acid has great potential in the fields of packaging materials and medical high polymer materials.

Claims

1. An organic frame material having isopoly-molybdic acid metal for manufacturing polylactic acid, the organic frame material having isopoly-molybdic acid metal having a chemical formula of [Cu(tfbtb).sub.0.5(β-Mo.sub.8O.sub.26)0.5(H.sub.2O)], wherein tfbtb is a 2,3,5,6-tetrafluoro-bis (1,2,4-triazole-1-methyl) benzene ligand, [β-Mo.sub.8O.sub.26] is β type octamolybdate anion.

2. The organic frame material having isopoly-molybdic acid metal for manufacturing polylactic acid of claim 1, wherein the organic frame material having isopoly-molybdic acid metal has a secondary structural unit being a triclinic crystal system, a space group of P-1, a molecular formula of C.sub.6H.sub.6CuF.sub.2Mo.sub.4N.sub.3O.sub.14, a molecular weight of 829.44, cell parameters of a = 8.0830(6) Å, b = 8.1875(6) Å, c = 13.0890(9) Å, α = 82.071(6)°, β = 79.008(6)°, γ = 78.452(6)°, a cell volume of 828.62(11) Å.sup.3, Z = 2, and the organic frame material having isopoly-molybdic acid metal has a basic structure of a three-dimensional network structure of a copper ion coordinating with 2,3,5,6-tetrafluoro-bis (1,2,4-triazole-1-methyl) benzene and molybdate radical [β-Mo.sub.8O.sub.26].

3. A method of manufacturing the organic frame material having isopoly-molybdic acid metal for manufacturing polylactic acid of claim 1 comprising: adding a copper salt, sodium molybdate dihydrate, 2,3,5,6-tetrafluoro-bis (1,2,4-triazole-1-methyl) benzene and distilled water into a reactor; heating the reactor in an oven for a period of time to form a mixture; cooling the reactor to the room temperature; performing dry centrifugation to the mixture to obtain a crystal of the organic frame material having isopoly-molybdic acid metal; rinsing the crystal of the organic frame material having isopoly-molybdic acid metal with deionized water and ethanol; and drying the crystal of the organic frame material having isopoly-molybdic acid metal to obtain the organic frame material having isopoly-molybdic acid metal, wherein the reactor is heated in the oven at a temperature ranging between 140 and 180° C. for the period of time between 24 and 72 hours.

4. The method of claim 3, wherein the copper salt is selected from any one or more of copper nitrate, copper acetate and copper sulfate.

5. The method of claim 3, wherein the mass ratio between the copper salt and the sodium molybdate dihydrate is between 1:1 and 1:2.

6. The method of claim 3, wherein the mass ratio between the 2,3,5,6-tetrafluoro-bis (1,2,4-triazole-1-methyl) benzene and the copper salt is between 1:2 and 1:6.

7. The method of claim 3, wherein the ratio between the 2,3,5,6-tetrafluoro-bis (1,2,4-triazole-1-methyl) benzene and the sodium molybdate dihydrate is between 1:2 and 1:8.

8. The method of claim 3, wherein each 0.01 mmol of 2,3,5,6-tetrafluoro-bis (1,2,4-triazole-1-methyl) benzene corresponds to 4 to 7 ml water.

9. An application of the organic frame material having isopoly-molybdic acid metal for manufacturing polylactic acid of claim 1 in a ring opening polymerization of lactide comprising: adding the organic frame material having isopoly-molybdic acid metal and lactide into a dry Schlenk reaction tube; and effecting a bulk ring opening polymerization under a reaction temperature to obtain the polylactic acid, wherein the reaction temperature is between 150 and 190° C., and a reaction time is between 2 and 12 hours.

10. The application of claim 9, wherein the ratio between the organic frame material having copper containing isopoly-molybdic acid metal and lactide is between 1:500 and 1:5000, the weight average molecular weight of the polylactic acid is between 60,000 and 90,000, and the molecular weight distribution index is between 1.3 and 1.6.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below. It is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise, in which:

[0023] FIG. 1 is a diagram showing the coordination environment of copper ions in the organic frame material having copper containing isopoly-molybdic acid metal according to an embodiment of the present invention;

[0024] FIG. 2 is a schematic three-dimensional network structure diagram showing the organic frame material having copper containing isopoly-molybdic acid metal according to an embodiment of the present invention;

[0025] FIG. 3 is a powder diffraction diagram of the organic frame material having copper containing isopoly-molybdic acid metal according to an embodiment of the present invention;

[0026] FIG. 4 is a thermogravimetric diagram of the organic frame material having copper containing isopoly-molybdic acid metal according to an embodiment of the present invention; and

[0027] FIG. 5 is a graph showing the conversion rate and reaction time of ring-opening polymerization of lactide catalyzed by the organic frame material having copper containing isopoly-molybdic acid metal according to an embodiment of the present invention.

DETAILED DESCRIPTION

[0028] In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.

[0029] In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.

Example 1

[0030] Manufacturing of the organic frame material having copper containing isopoly-molybdic acid metal: Copper nitrate trihydrate (19.3 mg, 0.08 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (19.4 mg, 0.08 mmol) and deionized water (12 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 160° C. for 48 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 52.4% (8.8 mg, based on Mo).

[0031] Infrared data (KBr, cm.sup.-1) are 3443 br, 3149 w, 1637 w, 1535 w, 1498 m, 1448 w, 1377 w, 1296 w, 1282 w, 1211 w, 1131 m, 1036 m, 995 s, 945 s, 906 s, 838 s, 734 s, 677 W, 660 m, 640 m, 567 s, 517 m, 448 m.

Example 2

[0032] Copper acetate monohydrate (16 mg, 0.08 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (19.4 mg, 0.08 mmol) and deionized water (12 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 160° C. for 48 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 42.7% (7.1 mg, based on Mo).

Example 3

[0033] Copper sulfate pentahydrate (20 mg, 0.08 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (19.4 mg, 0.08 mmol) and deionized water (12 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 160° C. for 48 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 43.3% (7.2 mg, based on Mo).

Example 4

[0034] Copper acetate monohydrate (8 mg, 0.04 mmol), copper sulfate pentahydrate (10 mg, 0.04 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (19.4 mg, 0.08 mmol) and deionized water (12 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 160° C. for 72 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 43.7% (7.3 mg, based on Mo).

Example 5

[0035] Copper nitrate trihydrate (9.65 mg, 0.04 mmol), copper sulfate pentahydrate (10 mg, 0.04 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (19.4 mg, 0.08 mmol) and deionized water (12 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 160° C. for 72 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 39.6% (6.6 mg, based on Mo).

Example 6

[0036] Copper acetate monohydrate (8 mg, 0.04 mmol), copper nitrate trihydrate (9.65 mg, 0.04 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (19.4 mg, 0.08 mmol) and deionized water (12 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 160° C. for 72 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 42.5% (7.1 mg, based on Mo).

Example 7

[0037] Copper nitrate trihydrate (9.65 mg, 0.04 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (19.4 mg, 0.08 mmol) and deionized water (12 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 160° C. for 48 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 42.8% (7.2 mg, based on Mo).

Example 8

[0038] Copper nitrate trihydrate (29 mg, 0.12 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (19.4 mg, 0.08 mmol) and deionized water (12 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 160° C. for 48 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 39.9% (6.7 mg, based on Mo).

Example 9

[0039] Copper nitrate trihydrate (19.3 mg, 0.08 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (9.7 mg, 0.04 mmol) and deionized water (12 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 160° C. for 48 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 43.9% (7.4 mg, based on Mo).

Example 10

[0040] Copper nitrate trihydrate (19.3 mg, 0.08 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (38.8 mg, 0.16 mmol) and deionized water (12 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 160° C. for 48 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 48.6% (8.2 mg, based on Mo).

Example 11

[0041] Copper nitrate trihydrate (19.3 mg, 0.08 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (29.1 mg, 0.12 mmol) and deionized water (12 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 160° C. for 48 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 45.6% (7.6 mg, based on Mo).

Example 12

[0042] Copper nitrate trihydrate (29 mg, 0.12 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (38.8 mg, 0.16 mmol) and deionized water (12 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 160° C. for 48 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 49.5% (8.4 mg, based on Mo).

Example 13

[0043] Copper nitrate trihydrate (19.3 mg, 0.08 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (19.4 mg, 0.08 mmol) and deionized water (8 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 160° C. for 48 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 42.7% (7.2 mg, based on Mo).

Example 14

[0044] Copper nitrate trihydrate (19.3 mg, 0.08 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (19.4 mg, 0.08 mmol) and deionized water (14 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 160° C. for 48 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 38.5% (6.5 mg, based on Mo).

Example 15

[0045] Copper nitrate trihydrate (19.3 mg, 0.08 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (19.4 mg, 0.12 mmol) and deionized water (12 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 140° C. for 48 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 46.8% (7.9 mg, based on Mo).

Example 16

[0046] Copper nitrate trihydrate (19.3 mg, 0.08 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (19.4 mg, 0.12 mmol) and deionized water (12 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 180° C. for 48 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 50.8% (8.5 mg, based on Mo).

Example 17

[0047] Copper nitrate trihydrate (19.3 mg, 0.08 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (19.4 mg, 0.08 mmol) and deionized water (8 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 160° C. for 24 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 48.1% (6.4 mg, based on Mo).

Example 18

[0048] Copper nitrate trihydrate (19.3 mg, 0.08 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (19.4 mg, 0.08 mmol) and deionized water (14 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 160° C. for 72 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 49.3% (8.3 mg, based on Mo).

Example 19

[0049] Copper nitrate trihydrate (19.3 mg, 0.08 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (19.4 mg, 0.08 mmol) and deionized water (12 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 140° C. for 72 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 48.4% (8.1 mg, based on Mo).

Example 20

[0050] Copper nitrate trihydrate (19.3 mg, 0.08 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (19.4 mg, 0.08 mmol) and deionized water (12 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 180° C. for 24 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 45.7% (7.6 mg, based on Mo).

Example 21

[0051] Copper nitrate trihydrate (19.3 mg, 0.08 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (29.1 mg, 0.12 mmol) and deionized water (12 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 140° C. for 24 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 39.4% (6.6 mg, based on Mo).

Example 22

[0052] Copper nitrate trihydrate (19.3 mg, 0.08 mmol), tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (29.1 mg, 0.12 mmol) and deionized water (8 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 180° C. for 72 hours, it is slowly cooled to room temperature at the rate of 5° C./hour to obtain green block crystals. The yield is 47.2% (8.8 mg, based on Mo).

Comparative Example 1

[0053] The copper salt is replaced with other metal salts (such as calcium nitrate, magnesium nitrate, aluminum nitrate, iron nitrate, cobalt nitrate or nickel nitrate, 0.4 mmol). The other metal salts, tfbtb (6.24 mg, 0.02 mmol), sodium molybdate dihydrate (19.4 mg, 0.08 mmol) and deionized water (12 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 160° C. for 48 hours, it is slowly cooled to room temperature at the rate of 5° C./hour. No crystal sample suitable for X-ray single crystal analysis is obtained. The product is amorphous powders with undefined structure.

Comparative Example 2

[0054] Sodium molybdate dihydrate is replaced with other molybdenum salts (such as ammonium molybdate or phosphomolybdic acid, 0.08 mmol). The other molybdenum salts, copper nitrate trihydrate (19.3 mg, 0.08 mmol), tfbtb (6.24 mg, 0.02 mmol) and deionized water (12 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 160° C. for 48 hours, it is slowly cooled to room temperature at the rate of 5° C./hour. No crystal sample suitable for X-ray single crystal analysis is obtained. The product is amorphous powders with undefined structure.

Comparative Example 3

[0055] Tfbtb is replaced with imidazole ligands (such as imidazole, 2-methylimidazole or benzimidazole, 0.02 mmol,). The imidazole ligands, copper nitrate trihydrate (19.3 mg, 0.08 mmol), sodium molybdate dihydrate (19.4 mg, 0.08 mmol) and deionized water (12 ml) are added to an 18 ml polytetrafluoroethylene autoclave. After the mixture undergoes a reaction at 160° C. for 48 hours, it is slowly cooled to room temperature at the rate of 5° C./hour. No crystal sample suitable for X-ray single crystal analysis is obtained. The product is amorphous powders with undefined structure.

Example 23

[0056] The organic frame material having copper containing isopoly-molybdic acid metal prepared in Example 1 is characterized as follows.

[0057] (1) Crystal structure determination of organic frame material having copper containing isopoly-molybdic acid metal.

[0058] The crystal structure is determined by a Bruker Apex II CCD diffractometer with graphite monochromated Mo Kα ray (λ = 0.71073 Å) at 293(2)K by ω scanning to collect the diffraction points. The collected data are restored by a SAINT program, and semi empirical absorption correction is performed by SADABS method.

[0059] The structure analysis and refinement are completed by SHELLXS and SHELLXL of SHELLXTL program respectively. F.sup.2 is modified by a full matrix least square method to obtain the coordinates and anisotropy parameters of all non-hydrogen atoms. All hydrogen atoms are theoretically fixed to the parent atom in the process of structural refinement, and the isotropic displacement parameter is slightly larger than the parent atom displacement parameter (C - H, 1.2, or N - H, 1.2 times). Table 1 shows detailed crystal measurement data.

[0060] Table 1 Crystallographic data of organic frame material having copper containing isopoly-molybdic acid metal

TABLE-US-00001 Molecular formula C.sub.6H.sub.6CuF.sub.2Mo.sub.4N.sub.3O.sub.14 Molecular weight 829.44 Crystal size 0.24 mm × 0.22 mm × 0.18 mm Crystallographic system triclinic Space group P-1 Cell parameters a = 8.0830(6) Å b = 8.1875(6) Å c = 13.0890(9) Å α = 82.071(6)° β = 79.008(6)° γ = 78.452(6)° Volume 828.62(11) Å.sup.3 Number of repeating units in cell 2 Density (calculated) 3.324 mg m.sup.-3 Absorption coefficient 4.313 Absorption correction Semi-empirical Refinement Least square F.sup.2 base fit 1.006 Final R factor [I >2σ(I)] R.sub.1 = 0.0277 R factor (all data) R.sub.1 = 0.0338 Residual error 0.745 eÅ-3 , -0.949 eÅ-3

[0061] FIG. 1 shows the coordination environment of the copper ions. FIG. 2 shows a three-dimensional network structure. FIG. 1 shows the coordination environment of the copper ions in an organic frame material having copper containing isopoly-molybdic acid metal. FIG. 2 shows a three-dimensional network structure diagram of an organic frame material having copper containing isopoly-molybdic acid metal.

[0062] (2) Characterization of phase purity of organic frame material having copper containing isopoly-molybdic acid metal

[0063] Turning to FIG. 3, the powder diffraction diagram of the organic frame material having copper containing isopoly-molybdic acid metal shows that it has a reliable phase purity, which ensures its catalytic activity in the ring-opening polymerization of lactide. (A RIGAKU d/max-2500 instrument is used.)

[0064] (3) Characterization of heat stability of organic frame material having copper containing isopoly-molybdic acid metal

[0065] The thermal stability of the organic frame material having copper containing isopoly-molybdic acid metal can be characterized by a thermogravimetric analyzer. The result shows the organic frame material having copper containing isopoly-molybdic acid metal has high heat stability up to 265° C. FIG. 4 shows the thermogravimetric diagram of the organic frame material having copper containing isopoly-molybdic acid metal (instrument model: NETZSCH/TG 209 F3).

Example 24

[0066] Using the organic frame material having copper containing isopoly-molybdic acid metal of Example 1 to catalyze lactide for the manufacturing of PLA

[0067] 2,880.00 mg lactide (20.00 mmol) and 8.3 mg organic frame material having copper containing isopoly-molybdic acid metal (0.01 mmol) are added to Schlenk reaction tubes. The tubes are heated to and remain at 180° C. for 6 hours to react. After the polymerization is completed, the product is cooled to room temperature. The product is dissolved in 15 ml dichloromethane. The organic frame material having copper containing isopoly-molybdic acid metal is recovered by centrifugation. Then, 60 ml of methanol is added to the filtrate to precipitate the polymer. The polymer is dried in a vacuum at 50° C. to obtain the white PLA product.

[0068] The relationship between the conversion rate and the reaction time is determined by .sup.1H NMR quantitative analysis, as shown in FIG. 5, which provides a graph of the conversion rate and reaction time of the organic frame material having copper containing isopoly-molybdic acid metal to catalyze the ring-opening polymerization of lactide (instrument model: Bruker AVANCE 400 MHz).

Example 25

[0069] 2,880.00 mg lactide (20.00 mmol) and 33.2 mg organic frame material having copper containing isopoly-molybdic acid metal (0.04 mmol) are added to Schlenk reaction tubes. The tubes are heated to and remain at 180° C. for 6 hours to react. After the polymerization is completed, the product is cooled to room temperature. The product is dissolved in 15 ml dichloromethane. The organic frame material having copper containing isopoly-molybdic acid metal is recovered by centrifugation. Then, 60 ml of methanol is added to the filtrate to precipitate the polymer. The polymer is dried in a vacuum at 50° C. to obtain the white PLA product.

Example 26

[0070] 2,880.00 mg lactide (20.00 mmol) and 4.15 mg organic frame material having copper containing isopoly-molybdic acid metal (0.004 mmol) are added to Schlenk reaction tubes. The tubes are heated to and remain at 180° C. for 6 hours to react. After the polymerization is completed, the product is cooled to room temperature. The product is dissolved in 15 ml dichloromethane. The organic frame material having copper containing isopoly-molybdic acid metal is recovered by centrifugation. Then, 60 ml of methanol is added to the filtrate to precipitate the polymer. The polymer is dried in a vacuum at 50° C. to obtain the white PLA product.

Example 27

[0071] 2,880.00 mg lactide (20.00 mmol) and 8.3 mg organic frame material having copper containing isopoly-molybdic acid metal (0.01 mmol) are added to Schlenk reaction tubes. The tubes are heated to and remain at 150° C. for 6 hours to react. After the polymerization is completed, the product is cooled to room temperature. The product is dissolved in 15 ml dichloromethane. The organic frame material having copper containing isopoly-molybdic acid metal is recovered by centrifugation. Then, 60 ml of methanol is added to the filtrate to precipitate the polymer. The polymer is dried in a vacuum at 50° C. to obtain the white PLA product.

Example 28

[0072] 2,880.00 mg lactide (20.00 mmol) and 8.3 mg organic frame material having copper containing isopoly-molybdic acid metal (0.01 mmol) are added to Schlenk reaction tubes. The tubes are heated to and remain at 190° C. for 6 hours to react. After the polymerization is completed, the product is cooled to room temperature. The product is dissolved in 15 ml dichloromethane. The organic frame material having copper containing isopoly-molybdic acid metal is recovered by centrifugation. Then, 60 ml of methanol is added to the filtrate to precipitate the polymer. The polymer is dried in a vacuum at 50° C. to obtain the white PLA product.

Example 29

[0073] 2,880.00 mg lactide (20.00 mmol) and 8.30 mg organic frame material having copper containing isopoly-molybdic acid metal (0.01 mmol) are added to Schlenk reaction tubes. The tubes are heated to and remain at 180° C. for 2 hours to react. After the polymerization is completed, the product is cooled to room temperature. The product is dissolved in 15 ml dichloromethane. The organic frame material having copper containing isopoly-molybdic acid metal is recovered by centrifugation. Then, 60 ml of methanol is added to the filtrate to precipitate the polymer. The polymer is dried in a vacuum at 50° C. to obtain the white PLA product.

Example 30

[0074] 2,880.00 mg lactide (20.00 mmol) and 8.30 mg organic frame material having copper containing isopoly-molybdic acid metal (0.01 mmol) are added to Schlenk reaction tubes. The tubes are heated to and remain at 180° C. for 12 hours to react. After the polymerization is completed, the product is cooled to room temperature. The product is dissolved in 15 ml dichloromethane. The organic frame material having copper containing isopoly-molybdic acid metal is recovered by centrifugation. Then, 60 ml of methanol is added to the filtrate to precipitate the polymer. The polymer is dried in a vacuum at 50° C. to obtain the white PLA product.

Example 31

Measurement of the Molecular Weight of the PLA of Example 24

[0075] 7.0 mg of PLA is taken and dissolved in 1 ml of tetrahydrofuran solution. The solution is filtered through a 0.4 .Math.m pore size polytetrafluoroethylene filter membrane. 20 .Math.l of the filtrate is taken and added to an LC-20AD GPC sampler produced by Shimadzu (Japan). The calculated weight average molecular weight is approximately 86,375, and the molecular weight distribution index is approximately 1.41.

[0076] Test conditions: The column temperature is 40° C. The eluent is tetrahydrofuran. The flow rate is 0.6 ml/min. The detector is a RID-10A detector. Calibration: four different standardized polystyrene having molecular weight ranging between 2,000 and 100,000 are used.

Measurement of the Molecular Weight of the PLA of Example 25

[0077] 7.0 mg of PLA is taken and dissolved in 1 ml of tetrahydrofuran solution. The solution is filtered through a 0.4 .Math.m pore size polytetrafluoroethylene filter membrane. 20 .Math.l of the filtrate is taken and added to an LC-20AD GPC sampler produced by Shimadzu (Japan). The calculated weight average molecular weight is approximately 81,013, and the molecular weight distribution index is approximately 1.53.

[0078] Test conditions: The column temperature is 40° C. The eluent is tetrahydrofuran. The flow rate is 0.6 ml/min. The detector is a RID-10A detector. Calibration: four different standardized polystyrene having molecular weight ranging between 2,000 and 100,000 are used.

Measurement of the Molecular Weight of the PLA of Example 26

[0079] 7.0 mg of PLA is taken and dissolved in 1 ml of tetrahydrofuran solution. The solution is filtered through a 0.4 .Math.m pore size polytetrafluoroethylene filter membrane. 20 .Math.l of the filtrate is taken and added to an LC-20AD GPC sampler produced by Shimadzu (Japan). The calculated weight average molecular weight is approximately 71,441, and the molecular weight distribution index is approximately 1.47.

[0080] Test conditions: The column temperature is 40° C. The eluent is tetrahydrofuran. The flow rate is 0.6 ml/min. The detector is a RID-10A detector. Calibration: four different standardized polystyrene having molecular weight ranging between 2,000 and 100,000 are used.

Measurement of the Molecular Weight of the PLA of Example 27

[0081] 7.0 mg of PLA is taken and dissolved in 1 ml of tetrahydrofuran solution. The solution is filtered through a 0.4 .Math.m pore size polytetrafluoroethylene filter membrane. 20 .Math.l of the filtrate is taken and added to an LC-20AD GPC sampler produced by Shimadzu (Japan). The calculated weight average molecular weight is approximately 63,871, and the molecular weight distribution index is approximately 1.55.

[0082] Test conditions: The column temperature is 40° C. The eluent is tetrahydrofuran. The flow rate is 0.6 ml/min. The detector is a RID-10A detector. Calibration: four different standardized polystyrene having molecular weight ranging between 2,000 and 100,000 are used.

Measurement of the Molecular Weight of the PLA of Example 28

[0083] 7.0 mg of PLA is taken and dissolved in 1 ml of tetrahydrofuran solution. The solution is filtered through a 0.4 .Math.m pore size polytetrafluoroethylene filter membrane. 20 .Math.l of the filtrate is taken and added to an LC-20AD GPC sampler produced by Shimadzu (Japan). The calculated weight average molecular weight is approximately 68,710, and the molecular weight distribution index is approximately 1.52.

[0084] Test conditions: The column temperature is 40° C. The eluent is tetrahydrofuran. The flow rate is 0.6 ml/min. The detector is a RID-10A detector. Calibration: four different standardized polystyrene having molecular weight ranging between 2,000 and 100,000 are used.

Measurement of the Molecular Weight of the PLA of Example 29

[0085] 7.0 mg of PLA is taken and dissolved in 1 ml of tetrahydrofuran solution. The solution is filtered through a 0.4 .Math.m pore size polytetrafluoroethylene filter membrane. 20 .Math.l of the filtrate is taken and added to an LC-20AD GPC sampler produced by Shimadzu (Japan). The calculated weight average molecular weight is approximately 67,196, and the molecular weight distribution index is approximately 1.49.

[0086] Test conditions: The column temperature is 40° C. The eluent is tetrahydrofuran. The flow rate is 0.6 ml/min. The detector is a RID-10A detector. Calibration: four different standardized polystyrene having molecular weight ranging between 2,000 and 100,000 are used.

Measurement of the Molecular Weight of the PLA of Example 30

[0087] 7.0 mg of PLA is taken and dissolved in 1 ml of tetrahydrofuran solution. The solution is filtered through a 0.4 .Math.m pore size polytetrafluoroethylene filter membrane. 20 .Math.l of the filtrate is taken and added to an LC-20AD GPC sampler produced by Shimadzu (Japan). The calculated weight average molecular weight is approximately 72,681, and the molecular weight distribution index is approximately 1.54.

[0088] Test conditions: The column temperature is 40° C. The eluent is tetrahydrofuran. The flow rate is 0.6 ml/min. The detector is a RID-10A detector. Calibration: four different standardized polystyrene having molecular weight ranging between 2,000 and 100,000 are used.

Comparative Example 4

[0089] 2,880.00 mg lactide (20.00 mmol) and 2.41 mg copper nitrate trihydrate (0.01 mmol) are added to Schlenk reaction tubes. The tubes are heated to and remain at 180° C. for 6 hours to react. The conversion rate is determined by .sup.1H NMR quantitative analysis. The calculated conversion rate is 62.7%. 7.0 mg of PLA is taken and dissolved in 1 ml of tetrahydrofuran solution. The solution is filtered through a 0.4 .Math.m pore size polytetrafluoroethylene filter membrane. 20 .Math.l of the filtrate is taken and added to an LC-20AD GPC sampler produced by Shimadzu (Japan). The calculated weight average molecular weight is approximately 10,863, and the molecular weight distribution index is approximately 1.58.

Comparative Example 5

[0090] 2,880.00 mg lactide (20.00 mmol) and 8.30 mg tfbtb (0.01 mmol) are added to Schlenk reaction tubes. The tubes are heated to and remain at 180° C. for 6 hours to react. The conversion rate is determined by .sup.1H NMR quantitative analysis. There is no conversion of lactide, and no PLA is obtained.

Comparative Example 6

[0091] 2,880.00 mg lactide (20.00 mmol) and 2.43 mg sodium molybdate dihydrate (0.01 mmol) are added to Schlenk reaction tubes. The tubes are heated to and remain at 180° C. for 6 hours to react. The conversion rate is determined by .sup.1H NMR quantitative analysis. The conversion rate is exceptionally low. The monomer conversion rate is 9%, the weight average molecular weight is 780, and the molecular weight distribution index is 1.12.

[0092] The present invention provides an organic frame material having isopoly-molybdic acid metal for manufacturing polylactic acid, and a method of manufacturing the same is provided. The chemical formula of the organic frame material having isopoly-molybdic acid metal is [Cu(tfbtb).sub.0.5(β-Mo.sub.8O.sub.26)0.5(H.sub.2O)]. tfbtb is a 2,3,5,6-tetrafluoro-bis (1,2,4-triazole-1-methyl) benzene ligand, and [β-Mo.sub.8O.sub.26] is a β type octamolybdate anion. Sodium molybdate dihydrate, copper salt and organic ligand 2,3,5,6-tetrafluoro-bis (1,2,4-triazole-1-methyl) benzene undergo hydrothermal reaction in a closed condition to form the organic frame material having copper containing isopoly-molybdic acid metal that has a three-dimensional structure. The synthesis method is simple with high yield and reproducibility. The organic frame material having isopoly-molybdic acid metal shows high catalytic activity towards the ring-opening polymerization of lactide. The resulting polylactic acid has a weight average molecular weight exceeding 60,000. The polylactic acid has great potential in the fields of packaging materials and medical high polymer materials.

[0093] It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the further embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.

[0094] As used herein, terms “approximately”, “basically”, “substantially”, and “about” are used for describing and explaining a small variation. When being used in combination with an event or circumstance, the term may refer to a case in which the event or circumstance occurs precisely, and a case in which the event or circumstance occurs approximately. As used herein with respect to a given value or range, the term “about” generally means in the range of ±10%, ±5%, ±1%, or ±0.5% of the given value or range. The range may be indicated herein as from one endpoint to another endpoint or between two endpoints. Unless otherwise specified, all the ranges disclosed in the present disclosure include endpoints. The term “substantially coplanar” may refer to two surfaces within a few micrometers (.Math.m) positioned along the same plane, for example, within 10 .Math.m, within 5 .Math.m, within 1 .Math.m, or within 0.5 .Math.m located along the same plane. When reference is made to “substantially” the same numerical value or characteristic, the term may refer to a value within ±10%, ±5%, ±1%, or ±0.5% of the average of the values.